Collection, Release, and Detection of Analytes with Polymer Composite Sampling Materials

ABSTRACT

A unique fiber core sampler composition, related systems, and techniques for designing, making, and using the same are described. The sampler is used to interface with existing field instrumentation, such as Ion Mobility Spectrometer (IMS) equipment. Desired sampler characteristics include its: stiffness/flexibility; thermal mass and conductivity; specific heat; trace substance collection/release dependability, sensitivity and repeatability; thickness; reusability; durability; stability for thermal cleaning; and the like. In one form the sampler has a glass fiber core with a thickness less than 0.3 millimeter that is coated with a polymer including one or more of: polymeric organofluorine, polyimide, polyamide, PolyBenzImidazole (PBI), PolyDiMethylSiloxane (PDMS), sulfonated tetrafluoroethylene (PFSA) and Poly(2,6-diphenyl-p-phenylene Oxide) (PPPO). Multiple polymer coatings with the same or different polymer types may be included, core/substrate surface functionalization utilized, and/or the core/substrate may be at partially filled with thermally conductive particles.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is related to commonly owned U.S. patentapplication Ser. No. 13/450,343 to Addleman et al. filed 18 Apr. 2012and issued 3 Feb. 2015 as U.S. Pat. No. 8,943,910 B2, which is herebyincorporated by reference as if set forth herein in its entirety(alternatively designated the '910 patent); however, to the extent thereis any conflict between the present application and the '910 patent, thepresent application prevails.

STATEMENT REGARDING RIGHTS TO INVENTION MADE UNDER FEDERALLY-SPONSOREDRESEARCH AND DEVELOPMENT

This invention was made with Government support under ContractDE-AC05-76RLO1830 awarded by the U.S. Department of Energy. TheGovernment has certain rights in the invention.

BACKGROUND

The present application relates generally to unique techniques, systems,methods, and devices for the collection, release, extraction and/ordetection of analytes; and more particularly, but not exclusively,relates to the composition, and other features of analyte samplingdevices; methods of designing, making, and using analyte samplers;analyte sampler kitting; and related systems.

State-of-the-art detection of explosives, illegal pharmaceuticals,poisons, radioactive materials, heavy metals, and otherchemically/biologically active substances, often involves trace analytecollection by physically wiping/swiping a test article surface with aswipe sampler that is submitted to on-site or remote instrumentation foranalysis. Still other arrangements, such as walk-through portals, maygenerate/direct certain airstreams to facilitate analyte collection.Even so, such alternatives still often rely on a sampling device that isthe same or at least similar to a swiping sampler to ultimately hold thecollected analyte(s) until transfer/release for instrumentationprocessing can take place.

Accordingly, the proper collection, retention, release, handling,transfer, extraction and processing of contraband or undesirablesubstance traces with sampling devices is often of paramount concern.When used for transportation security screening, the sampling deviceshould accommodate articles common to travel, which exhibit widevariation in terms of internal and external surface compositions andshapes desired to be sampled—posing significant challenges particularlyto swipe sampler designers.

Current trace detection samplers are often made of a cotton material,like muslin, and submit the trace agent(s) to Ion MobilitySpectrometer/Spectroscopy (IMS) field equipment for analysis. Typically,IMS enables rapid analysis, has low detection limits for many analytesof interest, has a low operating cost, and requires little or no samplepreparation. Consequently, IMS is one of the most widely used analyticalmethods for explosives detection throughout the world. However, IMS canproduce erroneous results due to its lack of selectivity, susceptibilityto interference, environmental humidity sensitivity, as well asnonlinear behaviors including, e.g., sample reproducibility issues, andhuman error.

Muslin cotton swipe material is often used to obtain samples forevaluation by a number of analytical instruments, such as MassSpectroscopy (MS), thermal desorption Gas Chromatography (TD-GC), X-RayFluorescence (XRF), Inductively Coupled Plasma Mass Spectrometry(ICP-MS), and extracted uranium detection techniques. For IMSapplications, recovery of the analyte from cotton/muslin sampling mediacan be accomplished by rinsing with solvents; however, it is lesscomplicated to heat the sampling media to introduce the analyte into theIMS for subsequent assay. Unfortunately, heat-based release fromcellulosic fibers, like cotton, is often constrained because thesefibers have a limited thermal stability—decomposing at the relativelylow temperature of about 150° C. Furthermore, unprocessed cottonsampling swabs contain non-cellulosic compounds found in the nativefibers (i.e. waxes, natural oils and starches) as well as sizing agentsand lubricants added for textile processing. Typically, processes usedto remove these impurities in industry include mechanical scouring,chemical scouring agents, and enzymatic methods that can weaken thecellulosic fibers and make them unsuitable for repetitious use.Moreover, natural sampling materials can have variable backgrounds andvariable chemical reactivity because of differences in natural growingprocesses and material sourcing from different geographic areas. Incontrast, synthetic sampling materials, like certain polymeric coatings,can be produced under controlled conditions minimizing backgroundinfluence and variation from other sources using process controltechniques. Various coatings can also improve uniformity. Thedecomposition of unstable swab material can release contaminants into adetection instrument and therefore interfere with the sample analysisand negatively impact the detection process. Also, high specific heat(>1.3 J/g ° C.), low thermal conductivity (˜0.24 W/m-K), and surfacechemical heterogeneity of cellulosic fiber materials can adverselyimpact the release of analytes from the surface—concomitantly limitingdetection performance.

U.S. Pat. No. 6,642,513 B1 to Jenkins et al. (the “'513 patent”), issuedon 4 Nov. 2003, offers several different alternatives to muslin samplingin the form of variously configured “traps,” and is hereby incorporatedby reference as if set forth in its entirety herein except to the extentthe '513 patent conflicts with the present application, in which casethe present application prevails. In the '513 patent, one trap type forwalk-through portal applications uses directed airflow to move analytesfrom the subject to the trap. For this application, trap composition isstainless steel—apparently without any coating or other surfacetreatment. While Stainless steel was selected because of good analytecollection properties it was thought to be too abrasive forcontact/swipe type applications (See the '513 patent col. 3, lines48-63; and col. 5, line 46—col. 6, line 2). The '513 patent alsospecifies a polyamide fiber felt—apparently without any type of coatingor other surface treatment. The '513 patent also specifies a trap havingan open weave glass fiber coated by PolyTetraFluoroEthylene (PTFE).Furthermore, the coating is systematically roughened with an abrasive tocut through it and break/expose glass fibers. A scrubbing materialresults from the broken fibers that acts in substantially the samemanner as a brush—believed to be better for analyte collection (See the'513 patent FIG. 2 and accompanying text). Moreover, coating is sparselyapplied so that open spaces remain in the glass fiber web as defined bythe open weave. See, for example, the '513 patent FIGS. 2 and 3 andaccompanying text; and col. 2, lines 37-58.

Unfortunately, the '513 patent fails to specify or consider varioussalient characteristics of samplers, leaving to the imagination manyaspects significant to performance. Among its shortcomings, the '513patent proposes to improve collection by exposing glass fibers andleaving unclosed holes in the glass fiber web—potentially exposingbordering glass fibers. To the contrary, untreated glass fibers havebeen found to hamper the desired release of certain analyte(s) becausethey bind too strongly as empirically established in the description setforth hereinafter. The '513 patent is also silent as to desired thermalproperties regarding analyte release by thermal desorption, glass type,and the like.

Generally, existing sampling swipes, including more rigid types, arerelatively expensive and have poor thermal conductivity—typically havinga relatively thick polymer (like PTFE) coating. Such configurations canimpede analyte release by thermal desorption or otherwise diminishdesired signal level. Current sampling techniques also fail to readilyaccommodate testing for certain nonstandard analytes of interest such asthose associated with monitoring nuclear compliance programs and/orverifying compliance with heavy metal safety exposure standardsapplicable to mining and other industries. Conventionally, the samplingmaterial needs to be digested and its chemical signature excluded fromthe analysis for the target analyte(s)—costing precious time andlimiting the ability to obtain consistent results. Consequently, itwould be desirable to have a sampling device that does not require suchlengthy treatment to release analyte(s) of interest.

Improving sample collection and analyte transfer to instrumentationwould likely improve sensitivity, stability, and potentiallyselectivity—addressing many fundamental problems presently plaguingfield-deployed instruments expected to consistently detect traceanalytes using conventional swipes. Indeed, existing schemes often canbe cumbersome to use, and/or make it difficult to readily andconsistently obtain a satisfactory result in certain instances.Accordingly, there remains an ongoing demand for further contributionsin these technical arenas.

By way of transition from this background to other sections of thepresent application, one or more specific definitions, and anysub-definitions thereof, are set forth below and supplemented by exampleor further explanation where deemed appropriate. Among other things,these definitions are provided to: (a) resolve meaning sometimes subjectto ambiguity and/or dispute in the applicable technical field(s) and/or(b) exercise the lexicographic discretion of any named inventor(s), asapplicable:

1. “Percentage” or “percent” (%) as used herein defaults to percentageby weight of the referenced item relative to the whole (also designatedby “% wt”) unless a different basis is expressly indicated.

2. “Nanoparticle” means any particle having a maximum dimension in therange of about 1 nanometer through about 1000 nanometers (nm).

3. “Fabric” broadly refers to both nonwoven and woven types. Nonwoventypes include, but are not limited to: felts, knitting, braiding,plaiting, Chopped Strand Mat (CSM), velour, combinations of these, andany other nonwoven fabric type known to those skilled in the art at thetime of the present application filing. Woven fabric types encompassboth closed weave and open weave varieties and include, but are notlimited to: plain weaves, satin weaves (including, but not limited toHarness Satin (HS) weaves and crow(s) foot weave), twilled weaves,heddle weaves, herringbone weaves, houndstooth weaves, Dutch plainweaves, Dutch twilled weaves, reverse Dutch weaves, basket weaves, Lenoweaves, mock Leno weaves, gauze weaves, cross weaves, tablet weaves,DURAWEAVEs, hybrid weaves, weft-faced weaves, warp-faced weaves(backstrap weaves), gauze weaves, oxford weaves, pinpoint weaves, poplinweaves, pile weaves, knotted weaves, real weight weaves, combinations ofthese various weaves, and other weaves as are known to those skilled inthe art. Weave patterns are typically described in terms of warp andweft, which refer to relative position of the fibers used to create theweave pattern. Typically, warp fibers refer to lengthwise fibers held ina loom while the weft fibers interlace at right angles with warp fibers.The weft fibers typically are carried with a shuttle during loomoperation. The weft also may be referred to as filling, woof, and pick.

4. “Closed weave” means any weave other than an “open weave” includingthat referenced in the '513 patent; and/or means a weave that lacks apre-defined pattern of one or more openings through the fabric, whereeach such opening is wider than any fiber element bordering the same andthe weave is arranged so two adjacent fiber elements are held apart fromeach other to provide opening formation under nominal conditions.

5. As is known to those skilled in the art, “fiber glass” or“fiberglass” sometimes refers to Glass-Reinforced Plastic (GRP), whichoften includes a pultrusion of roves or other configuration of a glassin combination with an amount of organic polymer, binder, and/or resineffective to prepare a corresponding composite combination thereof.However, “fiber glass/fiberglass” is also sometimes used to refer toglass fibers without organic polymer/binder/resin constituent(s) and/orbefore combination with the same. This distinction occasionally relieson context—often resulting in some degree of ambiguity. In contrast,“glass fiber” is more commonly accepted to refer to fibers of glassabsent/before combination with organic polymer/binder/resinconstituent(s) (if ever to be so combined); and such terminology shallbe used to mean the same. If the term “fiber glass” or “fiberglass” isused herein, it shall have the same meaning as “glass fiber” set forthabove. Any reference to an organic polymer, binder, and/or resin incombination with “glass fiber” and/or “fiberglass/fiber glass” isexpressly stated herein and/or by utilizing the “glass-reinforcedplastic” (GRP) terminology.

6. “High Strength Glass” (HSG) means any non-crystalline solidcomposition (equivalently designated “glass” or “amorphous” composition)conforming to the following “HSG formula”: 50% wt to 100% wt of anycombination of aluminosilicate, aluminum silicate, and/or alumina/silicaconstituents (such as, for example, Al₂O₃.SiO₂,), 0% wt to 25% wt of anycombination of calcium oxide (CaO) and/or magnesium oxide (MgO), and 0%wt to 5% wt Boron oxide (such as, for example, B₂O₃), with any balanceconsisting of other constituents and/or any minor impurities. Thisdefinition includes any glass complying with the HSG formula before orafter any processing, including, but not limited to: furnace heating,floating on molten material to form sheet glass, ion implantation,molten salt bath exposure, annealing, coating, or the like. Thisdefinition also means any R-glass and/or S-glass as these terms arecommonly understood by those of ordinary skill in the art at the time offiling of the present application—even if not conforming to the HSGformula.

7. “Flexural modulus” is a measure of stiffness/rigidity/resistance tobending, and is defined as the result (in units of pressure) fromtesting in accordance with American Society for Testing and Materials(ASTM) Standard D790 of any released version in effect on or before thefiling of the present application. The flexural modulus is sometimescalled the “bending modulus” or the “elastic modulus;” however, theselast two terms tend to be applied inconsistently to other types ofmoduli, test procedures, and/or contexts, so they are not used herein.Flexural modulus corresponds to an intrinsic material property subjectto certain constraints/limitations—being the ratio of stress to strainin flexural deformation as obtained by a three-point test per ASTM D790.This test applies force to a beam of the material under test as it restson two supports. The test force is applied on the opposite side from thesupport contacts and at is positioned therebetween. The test beam has aspecified span (length) to depth ratio and is believed to reduce oreliminate the influence of extrinsic factors (such as shapes that mightimpart different degrees of stiffness) during otherwise uniform the testresults. For the purpose of the present application, to the extent thematerial under test includes reinforcing fibers that extend a greaterdistance (on average) along a specified direction, the beam shall beprepared so that such direction coincides with the beam span—applyingthe test force approximately perpendicular to and across these fibers.To the extent the fibers extend approximately the same distance inmultiple directions (as with a generally planar fabric), any of thesedirections may be oriented to coincide with the beam span for testingpurposes. Flexural modulus is similar to Young's modulus in somerespects and the two sometimes have values that are well within an orderof magnitude or for the same material (both in units of pressure);however, flexural modulus has become a common industry alternative toYoung's modulus for synthetic organic polymers and composites becausethese types of materials tend to have certain properties for whichYoung's modulus may not prove as readily obtainable, informative, orapplicable. To provide a few examples of flexural modulus, consider thefollowing approximations: (a) PTFE<0.5 GigaPascal (GPa); (b) 25% wtglass-filled PTFE≈1.3 GPa; (c) cardstock >2.7 GPa; (d) Polyvinylchloride(PVC)≈3.3 GPa; (e) Gold <4.5 GPa; and (f) 20% wt glass-filledpolycarbonate≈5.5 GPa as based on a literature search (citationsomitted).

8. “Metal” means any elemental metal, with or without any minorimpurities therein, and any metal alloy (defined below).

9. “Metalloid” refers to any of the following elements: aluminum,antimony, arsenic, astatine, boron, carbon (as further definedhereinafter), germanium, polonium, selenium, silicon, tellurium, orcombination thereof, with or without minor impurities therein. A carbonmetalloid includes any allotrope of carbon, but excludes any carbon atomto the extent it is an atomic constituent in an organic compoundrecognized as such in any International Union of Pure and AppliedChemistry (IUPAC) reference to organic nomenclature in effect on orbefore the filing of the present application. To dispel any doubt,aluminum is considered both a metal and a metalloid for the purposes ofthe present application.

10. “Metal alloy” means a compound comprised of a combination of two ormore different metals, a combination of at least one metal and at leastone metalloid, or any combination thereof, either with or without minorimpurities.

11. “Inorganic metallic material” means: (1) any inorganic substancewith at least a majority of the following properties: malleability;ductility; electrical conductivity; thermal conductivity; ability tomelt and/or fuse two or more portions of such substance together; shinyappearance/metallic luster to the extent not covered with a coating,compound, oxide, or other constituent altering visual appearance of thesame; and/or (2) any inorganic substance with one or more metals and/ormetalloids alone or as an atomic constituent of a salt, compound,molecule, complex, adduct, composite, anion, cation, or othercombination with a nonmetal and/or a non-metalloid atomic constituent.Accordingly, inorganic metallic material includes, but is not limitedto: any metal, metalloid, or metal oxide, and any glass, ceramic, orglass-ceramic having a metal or metalloid atomic constituent. To dispelany doubt, inorganic metallic material does not include anyorganometallic substance.

12. “Heavy metal” means certain metals and metalloids that have thepotential to seriously impact the environment (including flora andfauna, among other things) and/or the safety of humans including:arsenic, cadmium, mercury, lead, chromium, copper, zinc, nickel,selenium, silver, antimony, thallium, beryllium, and cobalt in anyelemental form with or without minor impurities; and/or any combinationor metal alloy thereof.

13. “Contraband or undesirable substance” means any potential nefarious,illegal, dangerous, or threat agent listed in the '910 patent (in itstext and/or accompanying figures), and/or any substance that belongs inone or more of the following categories: (a) explosives; (b) illegallytrafficked drugs; (c) chemical or biological warfare agents; (d) nerveagents; (e) pesticides; (f) pharmaceutical process contaminants; (g)environmental toxins; (h) heavy metals; (i) actinides; (j) radioisotopesof any element with the potential to seriously impact the environment(including flora and fauna, among other things) and/or human safety;and/or (k) a salt, compound, molecule, complex, metal alloy,combination, analogue, homologue, isomer, equivalent, adduct,derivative, hydrate, composite, and/or stimulant of any substance listedin the '910 patent (in accompanying text and/or figures), and/orbelonging to any of categories (a)-(j).

14. “Ammonium” broadly means any substance that includes: (a) anammonium cation (referring to the general structure NH₄ ⁺, for example);(b) like-charged amine including any such amine with primary, secondary,tertiary, or quaternary substituents; and/or (c) any salt, combination,compound, molecule, complex, equivalent, analogue, homologue, adduct,and/or, composite of any of the substances of the foregoing listings (a)and (b). In contrast, any reference to the chemical formula NH₄ ⁺ forthe cation alone or as part of another formula, such as (NH₄)₂CO₃, shallbe limited to the meaning of such formula and equivalents thereto asunderstood by those of ordinary skill in the art at the time of filingof the present application.

15. “Onium” broadly means any substance comprising: (a) ammonium; (b) acation formed by protonation (hydron addition) of a mononuclear parenthydride of: the nitrogen family (periodic table group 15), the oxygenfamily (periodic table group 16), or the halogen family (periodic tablegroup 17); (c) derivatives formed by substitution of any cation of theabove-listed parent substances of (a) & (b) by univalent groups, (thenumber of substituted hydrogen may be indicated by the adjectivesprimary, secondary, tertiary or quaternary); (d) derivatives formed bysubstitution of any cation of the above-listed parent substances of(a)-(c) by groups having at least two free valencies on the same atom;(e) independent of the meanings conveyed under the foregoing listings(a)-(d), onium cations shall also encompass any meaning conveyed by theonium nomenclature that follows in this listing, where such nomenclaturehas the meaning that would be understood by those of ordinary skill inthe art at the time of filing of the present application unlessexpressly stated to the contrary: alkanium, alkenium, alkynium,alkonium, alkenonium, alkynonium, arenium, amidium, (includingcarboxamidium, for example) oxonium (refers to any oxygen cation withthree bonds, including, but not limited to: hydronium, oxocarbenium,alkoxonium, triethyloxonium, methyloxonium, trimethyloxonium,trialkoxonium, oxatriquinane, and oxatriquinacene, for example),nitrenium (refers to NH₂ ⁺ or more generally R₂N⁺, for example),nitrilium (refers to any cation formed by protonation of a nitrile asrepresented by R—C≡N⁺H or R—C⁺═NH, where “R” is a functional group, oralkylation of a nitrile [RCNR′]⁺, where “R” and “R′” are functionalgroups, for example), nitronium (refers to NO₂ ⁺ formed by protonationof nitric acid or removal of an electron from the nitrogen dioxidemolecule, for example), nitrosonium (refers to NO⁺ and organicderivatives thereof, for example), iminium (refers to a protonated orsubstituted imine cation of the general structure [R¹R²C═NR³R⁴]⁺, whereR¹, R², R³ and R⁴ are functional groups, for example), iminylium (refersto the general structure R₂C═N⁺, where R is a functional group, forexample), nitrylium, carbonium (refers to any cation that has apentavalent carbon atom or a carbon atom of greater valency/coordinationnumber, including but not limited to: methanium (CH₅ ⁺), ethanium (C₂H₇⁺), alkanium, and any organic derivative thereof, for example),carbenium (refers to a molecule with a trivalent carbon atom orthree-coordinate carbon atom that bears a +1 charge, and any organicderivative thereof, for example), carbynium (refers to the radical H₂C.⁺and any organic derivative thereof, for example), arsonium, stibonium,halonium, selenonium, fluoronium, chloronium, bromonium, borenium,telluronium, iodonium, bismuthonium, germonium, stannonium, plumbonium,boronium, silanium, hydrogenonium (refers to trihydrogen cation orprotonated diatomic/molecular hydrogen, for example), hydrohelium,kryptonium, xeonium, phosphonium, sulfonium, aminodiazonium,hydrocyanonium, diazonium, pyridinium, pyrylium, hydrazinium, diazenium,silylium, and mercuronium; (f) any substance with multiple “onium”cation groups, such as a double onium ion, a triple onium ion, andgreater onium ion multiples (+2, +3, and greater charge, respectively)where “onium” complies with any meaning of the foregoing listings(a)-(e); and/or (g) any salt, complex, compound, molecule, combination,adduct, hydrate, equivalent, analogue, and/or homologue of any of thesubstances of the foregoing listings (a)-(f). From a theoreticalstandpoint, onium compounds/cations are counterparts to “ate”complexes/anions—such anions often being polyatomic. Further, oniumcations and ate anions can combine to form a wide range of commonlyavailable/known salts.

16. “Carbonate” broadly means: (a) any salt or ester of carbonic acid orcarbamic acid; (b) a carbonate anion (CO₃ ²⁻), bicarbonate anion (HCO₃⁻), polyvalent percarbonate anion species including both a carbonateanion moiety and an oxide anion moiety, divalent peroxocarbonate anion(CO₄ ²⁻), divalent peroxodicarbonate anion (C₂O₆ ²⁻), monovalenthydrogenperoxocarbonate anion (H—O—O—CO₂ ⁻), or carbamate anion (CH₂NO₂⁻), where it is understood that two or more of the carbonate,bicarbonate, and carbamate anion species may coexist at equilibrium insolution under certain circumstances; (c) a carbonate, bicarbonate,subcarbonate, percarbonate, peroxocarbonate, peroxodicarbonate, orsesquicarbonate anion constituent; and/or (d) any salt, complex,compound, molecule, combination, adduct, hydrate, equivalent, analogue,and/or homologue of any of the substances of the foregoing listings(a)-(c). In contrast, any reference to the chemical formula CO₃ ²⁻ forthe anion alone or as part of another formula, such as (NH₄)₂CO₃, shallbe limited to the meaning of such formula and equivalents thereto asunderstood by those of ordinary skill in the art at the time of filingof the present application.

17. “Thickness” refers to the smallest dimension of an object unlessexpressly indicated to the contrary herein. By way of example, thicknessrefers to the distance between opposing sides of a generally planarsampler, where such opposing sides have a length and width much greaterthan such distance (thickness). To the extent thickness isquantitatively specified herein, it is determined as the average of ten(10) measurements taken at ten (10) different locations along the objectusing a measurement device having a rated accuracy of +/−0.01 millimeter(mm) or better. As used herein, ‘thin” means at least a portion of anobject under measurement has a thickness of less than or equal to 0.3 mmdetermined in accordance with such measurements. As a corollary, to theextent used herein an object is “thick” if it is not “thin” such thatits thickness dimension is determined to be >0.3 mm as determined bymeasurements according to the procedure listed above. These definitionsof thin and thick supersede any definition of like terms set forth inthe '910 patent and/or the '513 patent.

18. To “calcine” (also calcined/calcining/calcination and the like)generally refers to heating a subject material in an enclosure at aselected temperature to remove a volatile fraction, desiccate, reduce,oxidize, and/or otherwise selectively change the subject material, andmay be performed with or without control of air, oxygen, or other gascontent in the enclosure in its broader form. By way of nonlimitingexample, for a composite subject material, heating temperature may beselected above the melting point of a polymer constituent (but notexceeding its decomposition temperature) while remaining below themelting point of a glass fiber fabric constituent to which the polymeris applied. The selected temperature completely or partially melts thepolymer constituent, changing its morphology to promote the formation oflonger polymeric molecules or “chains” and/or interconnection betweenthe same under certain circumstances, while the glass fabric is onlynegligibly impacted if at all (but note polymer coverage of the fabricand the polymer-glass interface may be subject to change by in thiscalcination example). At the same time, calcining may at least partiallyremove any volatile fraction present after certain liquid-basedapplication of the polymer to the fabric (even with pre-calcinationevaporation), and/or desiccate all of the constituents as a function ofconstituent composition, heating temperature selected, and/or heatingduration. Because calcination and roasting in a metallurgical/materialscience context are sometimes compared, it should be appreciated thatroasting is generally performed at a considerably higher temperaturethan calcination for a given material—where roasting typically heats anore to promote one or more gas-solid reactions that improve metalcomponent purity of/from the ore.

The above listing of one or more definitions/sub-definitions apply toany reference to the corresponding subject terminology herein unlessexplicitly set forth to the contrary. Any acronym, abbreviation, orterminology defined in parentheses, quotation marks, or the like shallhave the corresponding meaning imparted thereby through the presentapplication unless expressly stated otherwise herein.

SUMMARY

Among the embodiments of the present application are unique analytesampler compositions/configurations and related systems, apparatus,methods, kits, processes, and devices. Other embodiments include uniquetechniques to design, make, use, reuse, clean, and/or extract analytefrom an analyte sampler.

For some unique embodiments, it has been found a relatively stiff/rigidsampling swipe with suitable mechanical stability facilitates replicateuse and desired detector interfacing. It has also been unexpectedlydiscovered that sampler stiffness/rigidity can be controlled withincertain limits through the manner of application, concentration, andcomposition of polymer(s) applied to a sampler fiber core and thethermal treatment of the polymer(s) after initial deposition on thesampler fiber core. Additionally or alternatively, in other uniqueembodiments certain thermal characteristics/properties of a sampler areprovided that are conducive to thermal release of sampler-collectedanalyte(s) for analysis with existing instrumentation and/or facilitateat least partial thermal cleaning of such sampler with the same. As afurther alternative or additional aspect, it has been discovered that asampler with low surface energy/hydrophobic properties enables moreeffective release of certain sampler-collected analyte(s). Yet otherunique embodiments have been discovered conducive to extraction of heavymetals and actinides (especially uranium). In still other uniqueembodiments, a fabric sampler core is utilized with controlled thermalsintering, particulate addition, minimal polymer concentration, and/orchemical core treatment to enhance particle collection efficiency,polymer deposition/application, sampler thermal conductivity, and/or therelease of sampler analyte(s).

In another embodiment, a sampler includes a fabric core comprised of oneor more of: HSG, polymeric thermoplastic, polymeric thermoset, metal,metalloid, inorganic oxide, ceramic, and/or glass-ceramic; and a polymerapplied to the fabric core that includes at least one of the group of:polymeric organofluorine, polyamide, polyimide, PolyBenzImidazole (PBI),PolyDiMethylSiloxane (PDMS), sulfonated tetrafluoroethylene (PFSA), andPoly(2,6-diPhenyl-p-Phenylene Oxide) (PPPO). It should be appreciatedthat PPPO is also known by the trademark TENAX TA, and aPPPO/graphitized carbon combination (also known by the trademark TENAXGR) is encompassed by this listing given PPPO is a member of the polymerlisting and the TENAX GR combination. In one more particular form, thefabric core is comprised of one or more of: HSG, metal, metalloid, metaloxide, ceramic, and glass-ceramic. In still a more particular form, thefabric core is comprised of one or more of: HSG, carbon, metal, metaloxide, ceramic, and glass-ceramic. In yet a more specific form, thefabric core includes a metal oxide coated glass (such glass may be HSG,but is not limited to such type) and/or metal oxide coated metal asfurther described elsewhere herein. In still an even more specific form,the fabric core is comprised of HSG. The fabric core is comprised ofS-glass in an even more particular form. In other forms, the compositionof the polymer applied to any of the previously described fabric coreforms may be selected from any of the successively more specificlistings (a)-(e) as follows: (a) perfluorocarbon, perfluoroether,Ethylene-TetraFluoroEthylene copolymer (ETFE), EthyleneChloroTriFluoroEthylene copolymer (ECTFE),poly(tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride) (THV)copolymer, PolyVinylidene diFluoride (PVdF), FluorinatedEthylene-propylene (FEP), PolyChloroTriFluoroEthylene (PCTFE), PolyVinylFluoride (PVF), PolyTRiFluoroEthylene (PTRFE),poly(vinylidene-tetrafluoroethylene) copolymer,poly(vinylidene-trifluroethylene) copolymer, PPBI, PDMS, and PPPO; (b)perfluorocarbon, perfluoroether, ETFE, FEP, THV copolymer, PVdF, andPPPO; (c) perfluorocarbon, PerFluoroAlkoxy (PFA), ETFE, PVdF, and FEP(where “pefluoroether” is inclusive of PFA); (d) PFA, ETFE, FEP, andPTFE; and (e) PTFE.

Yet another embodiment is directed to a method of making a contraband orundesirable substance sampler, comprising: preparing the sampler with afabric core formed of fibers including one or more of: glass, metalloid,metal, inorganic oxide, ceramic, and glass-ceramic; heating the fabriccore to a first predefined temperature for a first predefined duration;applying a polymer to the fabric core to further prepare the sampler,the polymer being one or more of: polymeric organofluorine, polyamide,polyimide, PBI, PFSA, PDMS, and PPPO; controlling stiffness of thecontraband or undesirable substance sampler by: selecting a predefinedamount of the polymer for application to the fabric core, and regulatinga heat treatment of the sampler at a second predefined temperature for asecond predefined duration; and after the heat treatment, providing thesampler for application with detection instrumentation. Certain morespecific forms include: applying the polymer by depositing it on thefabric core from a liquid particulate dispersion of such polymer, atleast partially filling the fabric core with nanoparticles selected toprovide a desired thermal performance before applying the polymer,functionalizing at least a portion of the surface of the fabric corewith silane ligands before applying the polymer, and/or applying afurther polymer layer on the polymer applied to the fabric core, wherethe further polymer layer has a different composition than the polymerapplied to the fabric core in at least one particular embodiment. In onemore particular form, the fabric core composition may be selected fromany of the successively more specific listings (a)-(c): (a) HSG, metal,metalloid, inorganic oxide, ceramic, and glass-ceramic; (b) HSG,metalloid, metal, and metal oxide; and (c) HSG, carbon, metal, and metaloxide. In another specific form, the fabric core includes a metal oxidecoated glass (such glass may be HSG or a non-HSG type) and/or metaloxide coated metal. In still an even more specific form, the fabric coreis comprised of HSG. In yet an even more particular form, the fabriccore is comprised of S-glass. Other variations result by selecting thepolymer applied to any of the previously described fabric core forms maybe selected from any of the successively more specific listings (a)-(e)as presented in the immediately preceding paragraph. For the previouslydescribed forms that include at least partial filling of the fabriccore, the nanoparticle composition may be selected from any of thesuccessively more specific listings (a)-(e): (a) inorganic metallicmaterial; (b) one or more of metal, metal oxide, carbon, ceramic, andglass-ceramic; (c) one or more of metal, metal oxide, and carbon; (d)one or both of a nanotube or graphene allotrope of carbon; and (e)alumina.

Still a further embodiment detects a contraband or undesirablesubstance, comprising: collecting the contraband or undesirablesubstance with a sampler, including a woven fabric with a closed weaveand a first polymer layer deposited thereon to at least partially coverthe fabric, the fabric having a thickness of less than or equal to about0.3 mm and being comprised of one or more of: glass, metalloid, metal,inorganic oxide, ceramic, and glass-ceramic, and the first polymer layerbeing comprised of one or more of: polymeric organofluorine, polyamide,polyimide, PBI, PDMS, PFSA, and PPPO with a calcined content of lessthan or equal to 40%; transferring the contraband or undesirablesubstance from the sampler to detection instrumentation; and detectingthe contraband or undesirable substance with the instrumentation. Otherforms include, preparing the sampler by at least partially filling thefabric with nanoparticles selected to provide desired thermalperformance; applying a second polymer layer on the first polymer layer,which has a different composition than the first polymer layer incertain forms; and/or functionalizing at least a portion of the surfaceof the fabric by silanizing at least a portion of the fabric and thenanoparticles (if nanoparticles are present). In addition or as analternative to the previously described forms, still other embodimentsof the samplers have a thickness of less than or equal to 0.5 mminclusive of all polymer layers applied to the fabric, and/or thesampler has a flexural modulus selected from among the following ranges(a)-(c): (a) from about 0.75 GPa through about 10 GPa, (b) from about 1GPa through about 8 GPa, or (c) from about 2 GPa through about 6 GPa.

Another embodiment is directed to a kit to test for presence of one ormore contraband or undesirable substances, comprising: several samplerseach structured to collect the one or more contraband or undesirablesubstances and release the one or more contraband or undesirablesubstances for analysis, the samplers each including a woven fabric anda polymer applied thereto, the fabric having a thickness of less than orequal to about 0.3 mm and being comprised of one or more of: HSG,carbon, metal, ceramic, glass-ceramic, and metal oxide, and the polymerbeing comprised of one or more of: polymeric organofluorine, polyamide,polyimide, PBI, PDMS, PFSA, and PPPO; and a container with at least oneor more of the samplers enclosed therein.

A further embodiment is directed to substance detection that includes:collecting the substance with a three-dimensional collection framework,the framework including a support structure, the support structurecomprising one or more of: polymeric thermoplastic, polymeric thermoset,metal, metalloid, inorganic oxide, ceramic, and glass-ceramic; theframework including several recesses each defining an external openingfacing away from the framework, a polymer applied to at least partiallycoat the support structure, the polymer being comprised of one or moreof: polymeric organofluorine, polyamide, polyimide, PBI, PDMS, PFSA, andPPPO; transferring the substance from the collection framework todetection instrumentation; and detecting the substance with theinstrumentation.

Other features, aspects, forms, embodiments, applications,implementations, techniques, objects, benefits, advantages, options,methods, processes, apparatus, configurations, arrangements, components,systems, compositions, substitutions, and variations shall becomeapparent from the description and figures provided herewith.

BRIEF DESCRIPTION OF THE DRAWING(S)

FIG. 1 depicts a partially diagrammatic view showing a sampler-basedanalyte processing system of one embodiment of the present application.

FIG. 2 depicts a partially diagrammatic view illustrating a sampler kitthat can be used with the system of FIG. 1.

FIG. 3 depicts a partially diagrammatic view showing a handheld wand toreceive and operate with a sampler of the type shown in FIG. 1 or FIG.2.

FIG. 4 is a flowchart representing one process for making a sampleraccording to the present application.

FIGS. 5 & 5A-5D schematically represent a comparison of different weavepatterns with FIGS. 5A-5D in partial view form. FIG. 5 schematicallydepicts all the partial views of FIGS. 5A-5D to indicate relativeorientation among them. FIG. 5A provides a partial, schematic view of aplain weave in the upper right corner and three different Harness Satin(HS) weaves: 4 HS weave (or “crowfoot” weave) in the upper left corner,a 5 HS weave in the lower right corner, and an 8 HS weave in the lowerleft corner; FIG. 5B provides a partial, schematic view of Five-Heddle(FHD) weave (upper), Herringbone weave (middle), and 3/3 twilled weave(lower); FIG. 5C provides a partial, schematic view of 2/2 twilled weave(upper), Dutch plain weave (middle), and Dutch twilled weave (lower);and FIG. 5D provides a partial, schematic view of Leno weave (upper)(more specifically a form of gauze weave), mock Leno weave (middle), andbasket (panama) weave (lower). The weaves are depicted in FIGS. 5A-5Dwith disproportionate, exaggerated spacing between warp/weftconstituents to enhance clarity. The partial views of FIGS. 5A, 5B, and5D each depict a planar weave swatch and at least one representation ofa sectional/edge perpendicular to the swatch plane. FIG. 5C is a view ofweave patterns in perspective that conveys the same information as theswatch and sectional/edge representations of FIGS. 5A, 5B, and 5D.

FIG. 6 is a partially diagrammatic, cross-sectional view of the samplerof FIG. 1 that corresponds to the section line 6-6 of FIG. 1, it furtherincludes a partial cutaway that stair-steps down from the top toward theleft side.

FIG. 7 is a schematic, perspective view of an alternative samplerdepicting phenyl terminal groups in a functionalization sub-layer of theblock-represented core fabric that is covered by multiple polymerlayers.

FIG. 8 is a flowchart representing one process for using a sampleraccording to the present application.

FIG. 9 is a comparative graph of magnitude versus time of threedifferently-sourced samplers each in response to a 10 nanogram (ng) TNTsample. In top-to-bottom order of the inset legend: the “X” data pointplot represents the response of a sampler embodiment of the presentapplication—it has the highest peak, the “hollow triangle” (Δ) datapoint plot represents the response of a SAFRAN MORPHO brand of samplerwith an intermediate peak, and the “filled diamond” (♦) data point plotrepresents the response of a DSA DETECTION brand of sampler with thelowest peak.

FIG. 10 is a comparative graph of magnitude versus time responses offour PTFE-coated samplers with different cores each to a 10 ng TNTsample. In top-to-bottom order of the inset legend: the “filled diamond”(♦) data point plot represents the response of a stainless steel corewith the highest peak, the “filled circle” (●) data point plotrepresents the response of a thin S-glass core with the second highestpeak, the “filled square” (▪) data point plot represents the response ofa thick S-glass core with the third highest peak, and the “filledtriangle” (▴) data point plot represents the response of thickE-glass—it is the least responsive.

FIG. 11 is a comparative graph of magnitude versus time responses of twosamplers with different fabric core weaves to a 10 ng TNT sample. Intop-to-bottom order of the FIG. 11 inset legend: the “X” data point plotrepresents the response of a 4 HS weave pattern of thin E-glass with thehighest peak, and the “hollow triangle” (Δ) data point plot representsthe response of an 8 HS weave pattern of S-glass, which peaks at aslightly lower value. FIG. 11 includes inset computer-generated imagesof the 4 HS and 8 HS fabric weaves with like labeling.

FIG. 12 is a comparative graph illustrating magnitude versus timeresponses of four samplers with different heat treatments each to a 10ng TNT sample. In top-to-bottom order of the inset legend: the “hollowtriangle” (Δ) data point plot represents the response to about a 450° C.heat treatment, with the second highest peak; the “X” data point plotrepresents the response to about a 400° C. heat treatment, with thehighest peak; the “filled triangle” (▴) data point plot represents theresponse to about a 325° C. heat treatment, with the third highest peak;and the symbol of an “X” with a vertical line intersecting the “X”cross-point (similar to “*”) provides a data point plot of the responseto about a 150° C. heat treatment, with the lowest peak.

FIG. 13 is a computer-generated Scanning Electron Microscope (SEM) imageof a PTFE-coated sampler with S-type fiberglass core after heattreatment at about a 150° C. FIG. 14 is a computer-generated SEM imageof a PTFE-coated silicon wafer after heat treatment at about 150° C. forcomparison to FIG. 13.

FIG. 15 is a computer-generated SEM image of a PTFE-coated fabricsampler with an S-type fiberglass core after heat treatment at about325° C. FIG. 16 is a computer-generated SEM image of a PTFE-coatedsilicon wafer after heat treatment at about 325° C. for comparison toFIG. 15.

FIG. 17 is a computer-generated SEM image of a PTFE-coated fabricsampler with an S-type fiberglass core after heat treatment at about400° C. FIG. 18 is a computer-generated SEM image of a PTFE-coatedsilicon wafer after heat treatment at about 400° C. for comparison toFIG. 17.

FIG. 19 is a computer-generated SEM image of a PTFE-coated fabricsampler with an S-type fiberglass core after heat treatment at about450° C. FIG. 20 is a computer-generated SEM image of a PTFE-coatedsilicon wafer after heat treatment at about 450° C. for comparison toFIG. 19.

FIG. 21 is a comparative graph of magnitude versus time responses ofeach of three different PTFE-coated, S-type fiberglass core samplers,with and without phenyl surface functionalization, to a 10 ng TNTsample. In top-to-bottom order of the inset legend: the “X” data pointplot represents the response of a Phenyl-PTFE sampler heat-treated atabout 150° C.—it has the highest peak, the “hollow triangle” (Δ) datapoint plot represents the response of a Phenyl-PTFE sampler heat-treatedat about 400° C.—it has an intermediate peak, and the “hollow diamond”(⋄) data point plot represents the response of a PTFE sampler (no phenylor other functionalization type) heat-treated at about 400° C.—it hasthe lowest peak.

FIG. 22 is a diagrammatic, perspective view of a framework structureoutlining the shape of a truncated octahedron and corresponding to anintroductory, conceptual constituent of a substance collection frameworkof a 3-D (three-dimensional) sampler further shown in FIGS. 24 & 25.

FIG. 23 is a diagrammatic, perspective view of a solid geometryrepresentation of a bitruncated cubic honeycomb form of tessellation.FIG. 23 serves as a conceptual bridge from the framework structure ofFIG. 22 to the collection framework of FIGS. 24 & 25. The bitruncatedcubic honeycomb of FIG. 23 may be described as an arrangement of anumber of coincident, solid truncated octahedral blocks. Each of theseblocks correspond to the truncated octahedral shape outlined by theframework structure shown in FIG. 22. These truncated octahedral blocksare geometrically coincident and arranged so they merge along coincidentpairs of edges and vertices where brought together to correspond to thehoneycomb. As is common in the art, this figure is provided withgrayscale shading to enhance clarity of three-dimensional aspectsthereof.

FIG. 24 is a diagrammatic, perspective view of an openwork, 3-D,lattice/cage-like substance collection sampler with a collectionframework that corresponds to an open form of a bitruncated cubichoneycomb arrangement conceptually introduced in FIGS. 22 & 23. ThisFIG. 24 arrangement is of the same general type shown in FIG. 23;however, the number of coincident truncated octahedral-shapedconstituents and the overall shape differ. As is common in the art, thisfigure is provided with grayscale shading to enhance clarity ofthree-dimensional aspects thereof.

FIG. 25 is a diagrammatic, perspective view of a cross-sectioned portionof the three-dimensional sampler framework shown in FIG. 24—thecross-section being taken along a sectional plane approximately parallelto the view plane of FIG. 24. As is common in the art, this figure isprovided with grayscale shading to enhance clarity of three-dimensionalaspects thereof.

FIG. 26 is a comparative graph of percent (%) extraction efficiencyversus time for three different uranium compounds: uranium oxide (U₃O₈),uranyl fluoride (UO₂F₂), and uranyl nitrate (UO₂(NO₃)₂)—each of thesecompounds being extracted from a respective PTFE-coated sampler with 6.0molar (M) nitric acid aqueous solution. In top-to-bottom order of theinset trend line legend: the uniform dashed/hidden line style “

” represents a trend line plot for the response of U₃O₈, thephantom/cutting plane line style “

” represents a trend line plot for the response of UO₂F₂, and thechain/center line style “

” represents a trend line plot for the response of UO₂(NO₃)₂.

FIG. 27 is a comparative graph of percent (%) extraction efficiencyversus time for the three different uranium compounds of FIG. 26—each ofthese compounds being extracted from a respective PTFE-coated samplerwith a 1.0 M sodium carbonate aqueous solution. The same legend appliesas described for FIG. 26.

FIG. 28 is a comparative graph of percent (%) extraction efficiencyversus time for the three different uranium compounds of FIG. 26—each ofthese compounds being extracted from a respective PTFE-coated samplerwith a mixture of 1.0 M ammonium carbonate and 1.0 M hydrogen peroxidein aqueous solution. The same legend applies as described for FIG. 26.

DETAILED DESCRIPTION OF REPRESENTATIVE EMBODIMENTS

In the following description, numerous specific details are given toprovide a thorough understanding of the embodiments. One skilled in therelevant art will recognize, however, that the invention(s) of thepresent application can be practiced without one or more of the specificdetails, or with other methods, processes, compositions, arrangements,configurations, kits, systems, devices, apparatus, components,materials, etc. In other instances, well-known structures, materials, oroperations are not shown or described in detail to avoid obscuringaspects of the invention. Thus, for the purposes of promoting anunderstanding of the principles of each invention described or claimedherein, reference is made to representative embodiments illustrated inthe drawing(s) and specific language is used to describe the same. Anychanges, alterations, variations, modifications, reconfigurations,substitutions, implementations, differences, substitutions, andapplications of the principles of the same as described herein arecontemplated that would normally occur to one skilled in the art towhich they relate and/or that would become apparent from the descriptionand figures provided herewith—without departing from the scope of theinvention as set forth in the claims listed hereafter. By way ofnonlimiting example, in certain instances the description refers toexemplary explosive (like TNT), core composition (like S-glass), and/orpolymer applied to the core (like PTFE); however, the inventions definedby the claims are intended to cover any alternatives expressed thereinor covered thereby including any equivalents thereof. Accordingly, thisdescription of representative embodiments should be seen as illustrativeonly and not limiting the scope of any invention described and/orclaimed herein.

Among the embodiments of the present application are unique traceanalyte samplers, sampler kits, sampler devices, related systems, andmethods of designing, making and using samplers—including, but notlimited to release, removal, and/or extraction of analyte(s) of interestfrom a sampler. One sampler form includes a fabric substrate with aselected thickness to which a polymer is applied to provide a selecteddegree of stiffness/rigidity. The sampler stiffness can be expressed interms of flexural modulus, among other things, which can be controlledthrough the amount of polymer applied to the fabric substrate and heattreatment thereof. In some forms, a sampler core support structure iscomprised of one or more of: polymeric thermoplastic, polymericthermoset, glass, metal, metalloid, inorganic oxide, ceramic, andglass-ceramic. The core can have silane ligands bonded thereto for morereliable release of analyte(s) and/or to improve polymer applicationthereto. Alternatively or additionally, a sampler embodiment with awoven fiber core has a closed weave, thermally conductive particlesadded to the core; multiple polymer layers formed on the core, and/or atleast one layer of the polymer applied is comprised of one or more of:polymeric organofluorine, polyamide, polyimide, PBI, PDMS, PFSA, andPPPO.

FIG. 1 depicts another embodiment of the present application in the formof analyte processing system 20. System 20 is of a type that may be usedin an airport, train station, shipping port, or the like to performsecurity screening for contraband or undesirable substances. System 20includes analyte trace detection instrumentation 30, test article 50,and analyte collection sampler 100. Sampler 100 is of a thin, planarconfiguration. Instrumentation 30 includes a form of thermal desorptionIon Mobility Spectroscopy/Spectrometer (IMS) detector 32, and the testarticle 50 is further designated as being of a suitcase 52 form. Testarticle 50 includes outer surface 54 that may be smooth or rough toeither extent as might be expected for a standard suitcase 52. However,in other embodiments, a different type of test article 50 may includeone or more different surface qualities.

IMS detector 32 includes: operator display 34 to display relevantinformation regarding its operation; operator input control 36 in theform of a keyboard, touchscreen, mouse-like pointers, voice-activationinterface, touch keys, membrane switches, press buttons, sliders,toggle/rotary switches, dials, a combination of these, or the like; andintegral printer 38 with a print-out sheet 39 generated thereby. Inaddition to display 34, print-outs 39 from printer 38 can be used toinform the operator of results of analysis performed withinstrumentation 30; and instrumentation 30 may further be supplementedby an aural-output device to provide warnings, instructions, and thelike. Print-out 39 further provides a written record of the testingperformed with system 20. IMS detector 32 further includes sampler slot40, in which sampler 100 can be inserted for the release and transfer ofcollected analyte(s) by thermal desorption into IMS detector 32 foranalysis as further described hereinafter.

A different arrangement of operator input/output (I/O) may be providedsuch that there may be additional or alternative I/O devices withrespect to display 34, printer 38, and control 36. By way of nonlimitingexample, display 34 may be a touchscreen type without separate inputcontrol 36. IMS detector 32 embodiments are of any type suitable tosufficiency process samples, including, for example: those suitablemodels of IMS-based equipment from SARFAN MORPHO, SMITHS DETECTION, oranother supplier; and instrumentation combinations of IMS with otherdetector types, such as High-Performance Liquid Chromatography (HPLC),and the like. In still other embodiments, sampler 100 is utilized withnon-IMS detection equipment with appropriate alterations (if any) toprovide for proper analyte transfer/release and processing. Suchalternatives to IMS include: Thermal Desorption Gas Chromatographs(TD-GCs) and other GC types; liquid chromatography (LC) instrumentation;X-Ray Fluorescence (XRF); Inductively Coupled Plasma Mass Spectrometry(ICP-MS); gamma, beta, and alpha spectrometers and counting devices;Mass Spectrometry (MS) instrumentation; and combinations of thesevarious instruments including, e.g., Thermal Desorption GasChromatography Mass Spectrometers (TD-GCMS) and Headspace Analyzer GasChromatography Mass Spectrometers (HA-GCMS). Furthermore,instrumentation 30 may employ IMS or other equipment that receivessampler-released analyte(s) in a manner other than thermaldesorption—such as, analyte(s) released by sampler rinsing and/or otherapplication of one or more agents from which a detector sample isprepared. Any sample preparing rinse(s) and/or agent(s) can be of anytype suitable for the sampler type, substance(s) being detected, andsample composition requirements of the instrumentation used to detectsuch substance(s). In one example, an aqueous solution is used to rinsethe sampler and prepare the sample, and may be acidic or basic to adegree desired to facilitate sample preparation. In yet another form, amixture of an oxidizer (like hydrogen peroxide) and one or both of:onium and carbonate (like ammonium carbonate) in aqueous solution isutilized. Alternatively or additionally, one or more organic solventsmay be used to prepare the sample. To the extent a rinse, solution,and/or solvent is utilized, some form of agitation may be employed tofacilitate analyte release/extraction such as stirring, shaking,scrubbing, or the like. A Barringer IONSCAN 400A IMS (SMITHS DETECTION)was utilized in the following experimental examples 1-10, and is amongthe embodiments of IMS detector 32.

Sampler 100 is shown in a wiping/swiping position as applied to surface54 of suitcase 52 with an arrow indicating direction of the wipe/swipemotion to the right. The width W of sampler 100 along its longitude isindicated by double-headed arrow 102 and the length L of sampler 100 isindicated by double-headed arrow 104. FIG. 1 includes section line 6-6through sampler 100, with a corresponding cross-sectional view ofsampler 100 set forth in FIG. 6 to be discussed further hereinafter.

FIG. 2 illustrates kit 200 for use with system 20; where like referencenumerals refer to like features previously described. Kit 200 includesconsumable materials that may be desired to perform testing withdetector 32. All the items 202 of kit 200 may be provided together asshown in the depicted embodiment, or alternatively provided as a subsetof two or more items 202. Such multiple-item subsets also eachconstitute a type of “kit” as used herein. Kit 200 includes an outercontainer and/or packaging 201 that encloses various kit items 202.Various kit 200 instructions/directions may be provided on a surface ofpackaging 201 or on an inner surface, or separate sheet or card providedwith kit 200 that may be self-contained and/or may refer to an online,computer network accessible website as an additional or alternativesource for some or all of any remaining instruction, direction, and/orany update thereto.

Specifically, kit 200 includes multiple samplers 100 packaged togetherin container/package 101 that standing alone is also a form of kit.Container/package 101 includes related reference, instruction, and/ordirection 204 regarding use, warnings, or the like printed on itssurface. Samplers 100 may further include identifying marking,reference, instruction, and/or direction description directly thereon.Alternatively or additionally, some or the remainder of such informationmay be separately sourced from a sheet/card, packaging/containersurface, website, or the like as previously described in connection withkit 200 and packaging 201. Package 111 includes multiple calibrationstrips 110 with approximately the same form factor as samplers 100.Package 111 includes related reference, marking, and/or directions 112specific to calibrations strips 110 regarding use, warnings, or thelike. Strips 110 include a predefined type/quantity of substance tocalibrate detector 32. Package 121 also includes multiple verificationstrips 120 with approximately the same form factor as samplers 100.Package 121 includes related reference, marking, and directions 122specific to verification strips 120 regarding use, warnings, or the likeprinted on its surface. Strips 120 include a predefined type/quantity ofsubstance to verify proper calibration of detector 32 and can includeidentifying marking and direction description pertinent to the same.Samplers 100, strips 110, and/or strips 120 packaged in correspondingcontainers 101, 111, 121 comprise a subset of detector 32 interfaceconsumables, and each constitutes a kit individually, as do two or moreprovided collectively. Strips 110, 120 and/or package/container 111, 121may additionally or alternatively provide separate sourcing of some orthe remainder of instruction/direction information as previouslydescribed in connection with kit 200, samplers 100 and correspondingpackage and/or container.

Kit 200 also includes a subset of IMS consumables 220 directed toreplacement chemicals and hardware for detector 32. Without limitation,IMS consumables 220 include dopant 222 with directions 223 regardingidentity, use, warnings, or the like. In other embodiments, multipletypes of dopant may be included or obtained by kit or otherwise. IMSconsumables 220 further include IMS membranes 224 with directions 225regarding identity, use, warnings, or the like; and IMS filters 226 withdirections 227 regarding identity, use, warnings, or the like.Alternatively or additionally, IMS consumables 220 may includespecialized tools, O-rings, spare parts kits, a packet of samplecollection envelopes, maintenance/log books, fuses, dryer material,printer paper, analyte sampler release agent(s), and/or printer ink—justto name a few examples. Kit 200 further includes operator gloves 232contained in packaging 233. Packaging 233 includes related directions260 regarding identity, use, warnings, or the like. Gloves 232 are wornby operators to reduce the chance of contamination when collecting andhandling samplers 100, or strips 110, 120. Also included in kit 200 is apackage 235 of finger cots 234 that may be used as an alternative togloves 232. Package 235 includes related directions 270 regardingidentity, use, warnings, or the like. Kit 200 also includes cleaningdevices 236 in the form of a roll or other arrangement of multiplealcohol-soaked wipes to remove dirt, debris, and other detritus fromequipment and desired/surfaces likely to contaminate the samplingprocess. In other embodiments, different cleaning items may bealternatively or additionally included, such as cleaning swabs,separately packaged wipes, cleaning cloths, and/or containers ofcleaning solvent. Kit 200 also includes a can of pressurized air 238 toassist with keeping various surfaces clean. Another embodiment includesa powered air delivery device.

It should also be appreciated that gloves 232 or finger cots 234 (or aportion of either) may be configured to incorporate some or all of thematerials of sampler 100 (as described hereinafter). Accordingly, in afurther embodiment, it is envisioned that gloves 232 and/or finger cots234 (or a portion of either) each constitute a form of sampler(including some or all of sampler 100 features), that can be wiped onthe test article 50 to collect one or more analytes directly and thenrelease the collected analyte(s) for transfer to detector 32—it beingappreciated that detector 32 of system 20 likewise would be configuredto accommodate glove 232 and/or finger cots 234 functioning as samplers.Alternatively or additionally, gloves 232 or cots 234 may includedetachable/re-attachable sample-configured pieces (i.e. VELCO, reusableadhesives, or the like). The sampler 100 features incorporable withgloves 232 or cots 234 may include one or more of those previously orsubsequently described herein. Like previously described alternatives,kit 200 may be changed to match the particular consumables, tools, andthe like associated with the same.

FIG. 3 depicts mobile sampling wand 300; where like reference numeralsrefer to like features previously described. Wand 300 may be provided ina kit, as an accessory for detector 32, an option, or separately—to namejust a few examples. Wand 300 includes body 301 that is largely hollow.Body 301 is defined by shell 302 that includes surface 303. Body 301includes proximal end portion 301 a opposite distal end portion 301 b.Proximal end portion 301 b includes operator handle 310, and distal endportion 301 b defines vacuum intake opening 304. Within shell 302 is asuction-producing device 320. Device 320 can be powered by anelectrochemical cell, a battery of such cells, or a fuel cell—to name afew examples. In one form, wand 300 includes a power cable of suitablelength for mobile wand 300 operation—such cable receives electricityfrom a utility-sourced power outlet to power wand 300. Device 320 isoperatively connected to operator control 330. Operator control 330turns suction device 320 off and on, and optionally adjusts suctionspeed, reverses air flow direction, and the like.

Sampler 100 is mounted in sample chamber 340 defined by body 301 that isin fluid communication with opening 304, fluid pathways 350, and vents306. During operation, the suction device 320 is turned on via control330 to generate suction through opening 304 to move particles,volatiles, and/or other forms of analyte(s) of interest entrained in theresulting airflow for collection by sampler 100 in chamber 340. Airflowcontinues from opening 304/chamber 340 to discharge through wand vents306, being directed through pathways 350 in fluid communicationtherewith. Positioning of sampler 100 and suction airflow throughchamber 340 can influence the amount and type of analyte carrierscollected with sampler 100. In some forms, sampler 100 is configured asan air filtration device for such purposes.

Analyte(s) collected with sampler 100 may be transferred to detector 32by removing sampler 100 from wand 300 and inserting sampler 100 in slot40 for analyte release. Alternatively or additionally, collectedanalyte(s) may be transferred by reversing the airflow through wand 300so that pressurized air is directed through and/or over sampler 100 inchamber 240 and out of opening 304—carrying the collected analyte(s).For this embodiment opening 304 is connected/interfaced to detector 32to receive the sample by adaptive housing, hosing, or a similarmechanism. For this reversed air flow operation, the speed of the airmay be increased to assist with release from sampler 100. In one form,wand 300 includes a heating device (not shown) subject to control 330 toassist with the release of analyte(s) during reversed air flow.

FIG. 4 is a flowchart describing one nonlimiting process 400 for makingsampler 100 in various forms; where previously described referencenumerals refer to like features. Process 400 begins with sampler 100formation starting stage 402. From stage 402, process 400 continues withoperation 404. In operation 404, a sampler core/substrate material isselected and provided. The sampler substrate may take the form of one ormore pieces comprised of a synthetic and/or natural substance. Variousfactors may be of interest in selecting the sampler core/substratestructure and composition, including: sampler ease of use, relativecost, and material safety; any sampler constraints imposed by detectioninstrumentation requirements; sampler and core affinity for targetanalyte collection and retention, and ease of release/transfer of thesame to detection instrumentation; existence of any core filling,functionalization, and/or polymer coating, and to the extent inexistence, the composition and manner of application of the same;desired sampler and core surface homogeneity, smoothness, shape, or thelike; sampler definition of any external openings, recesses, passages,or the like; sampler thermal conductivity, specific heat, thermal mass(or thermal capacitance) or the like; sampler gas permeability; andsampler wear resistance, durability, cleaning, and the like relating tosampler reuse suitability—to name just a few.

Certain embodiments include a fibrous sampler core structure of anonfabric or fabric variety, while others include a nonfabric withoutfibers. Such nonfibrous cores may be comprised of one or more nonfibroussolid pieces or the like. In another form, the core is comprised of afibrous portion and nonfibrous portion. In fibrous embodiments, thefibers may be in the form of filaments, strands, yarn, threading, cord,roves, nanotubes, pultrusions, tows or the like; and may be categorizedas being a: nonfabric, nonwoven fabric, and/or woven fabric. Nonfabricfibrous configurations include conglomerations of fibers that may berandomly oriented in terms of direction or in an unbound unidirectionalconfiguration, and any other fiber arrangement that does not qualify asa fabric. Nonwoven fabric types include: spunlaced or any otherarrangement of fibers bound together through entanglement withoutweaving, Chopped Strand Mat (CSM), felts, knitting, braiding, plaiting,velour, leather, and/or by binding fibers together through applicationof pressure, thermal, chemical, adhesive, resin, organic polymer and/orsolvent treatment (either with or without a reinforcement backing), orany combination of these.

In certain embodiments, it has been surprisingly discovered that samplercore/substrate fibers of a fabric form have certain benefits. Woventypes of fabric include any type of fibers interlaced in accordance witha weave pattern. Such weave patterns include: plain weaves, satin weaves(including harness satin weaves and crow(s) foot weave), twill weaves,heddle weaves, herringbone weaves, houndstooth weaves, Dutch plainweaves, Dutch twilled weaves, reverse Dutch weaves, Basket weaves, Lenoweaves, mock Leno weaves, gauze weaves, cross weaves, tablet weaves,DURAWEAVEs, hybrid weaves, weft-faced weaves, warp-faced weaves(backstrap weaves), oxford weaves, pinpoint weaves, poplin weaves, pileweaves, real weight weaves, combinations of these various weaves, andother known weaves.

Referring additionally to the schematic view of FIG. 5 and thecorresponding partial views of 5A-5D, selected fabric weaves aredepicted and further described without limitation; where like referencenumerals previously described refer to like features. Several of thesefabric weave types are commonly used with inorganic fibers, such asvarious glasses and metals. Any of the depicted weave types may beutilized as a woven form of fabric core for sampler 100; however, theseweaves are not intended to exclude different weave types, embodimentswith a nonwoven fabric sampler, and/or nonfabric fiber sampler core.

FIG. 5 schematically illustrates the partial views of FIGS. 5A-5Dtogether and designates the contents as weave comparison 500—showing theorientation of the FIG. 5A-5D partial views relative to one another.Collectively, for each depicted weave of FIGS. 5A-5D, fibers 501 areinterlaced to provide fabric 502 generically designated by referencenumeral 502, which is also generically designated as substrate 503. InFIGS. 5A-5D, only a few of fibers 501 are specifically designated byreference numeral to preserve clarity. The collection, retention, andrelease of analyte(s) plus other aspects can vary with weave in terms ofeffective thickness, surface irregularity/roughness, fabricflexibility/stiffness, gas permeation, thermal desorption, solventextraction, strength, composition, and durability. Further factorsbearing on performance include: fiber thickness; filamentconfiguration/size; number of filaments per strand; strand weight/count;number of strands (un)twisted and/or number of strand plies in a yarn,thread, or cord; and yarn/thread/cord texture/size—to name only a fewexamples.

FIG. 5A depicts four different weave patterns of comparison 500. Plainweave 520 in the upper right corner schematically depicts the warp andweft fibers 501 of a plain weave pattern 526 to generically providefabric 502. Plain weave 520 is shown from two perspectives: Warp/weftrepresentation 522 and swatch 523. Representation 522 corresponds to across-section taken along section line 525. Due to the symmetry ofpattern 526, another representation is not shown to preserve clarity.Representation 522 is turned 90 degrees (to line-up with the thicknessprojecting perpendicular to the view plane) relative to the depiction ofswatch 523 parallel to the view plane to enhance understanding of weavepattern 526 by showing an edge-on/thickness view of the arrangement offibers 501 among other things. Typically, plain weave 520 is relativelytight—being a type of closed weave that readily allows adjacent fibersto come together in contact along at least a substantial portion of thefiber length—and likewise being inhospitable to the formation of anypattern-defined openings as is typical of an open weave.

FIG. 5A further schematically depicts three different types of harnesssatin weaves 505 of fibers 501 to provide corresponding substrates 503.In the upper left corner, 4 Harness Satin (HS) weave 510 schematicallydepicts the warp and weft of a 4 HS weave pattern 516 (also known as“crow(s)foot” weave). Weave pattern 516 is also representedschematically in FIG. 6 and designated as a type of fabric 502. 4 HSweave 510 is shown from three perspectives: swatch 513 parallel to theview plane, representation 512, and representation 514. Therepresentations 512 and 514 correspond to the perpendicular weft/warpinterlacing pattern 516 of fibers 501, and are turned 90 degreesrelative to swatch 513 along the corresponding swatch edges aspreviously described for weave 520. Representations 512 and 514 enhanceunderstanding of pattern 516 relative to swatch 513 by showing anedge-on/thickness view of pattern 516 and 4 HS weave 510 among otherthings. 4 HS weave 510 is typically a closed weave.

In the lower left corner of FIG. 5A, 8 HS weave 530 schematicallydepicts the warp and weft of an 8 HS weave pattern 536 of fibers 501 toprovide fabric 502 of substrate 503. 8 HS weave 530 is shown from threeperspectives: swatch 533 parallel to the view plane, representation 532,and representation 534. The representations 532 and 534 correspond tosections through weft/warp arrangement of pattern 536, and are turned 90degrees relative to swatch 533. Each representation 532, 534 is arrangedparallel to its section line/swatch edge and perpendicular to oneanother. Representations 532 and 534 enhance understanding of pattern536 relative to swatch 533 by showing an edge-on/thickness view of thearrangement of fibers 501 among other things. Typically, 8 HS weave 530is typically a closed weave.

In the lower right corner, 5 HS weave 540 schematically depicts the warpand weft of a 5 HS weave pattern 546 of fibers 501 to provide fabric502. 5 HS weave 540 is shown from three perspectives: swatch 543 alongthe view plane, representation 542, and representation 544, whichcorrespond to sections through the weft/warp arrangement of pattern 546,are turned 90 degrees relative to swatch 54, are aligned parallel to therespective sections and corresponding edges of swatch 543, and areperpendicular to each other. Representations 542 and 544 enhanceunderstanding of pattern 546 relative to swatch 543 by showing anedge-on/thickness view of the warp/weft arrangement of fibers 501, amongother things. Typically, 5 HS weave 540 is a closed weave.

FIG. 5B depicts three more weaves of comparison 500. The upper part ofFIG. 5B schematically depicts 5 Heddle (HFD) weave 550 comprised offibers 501 to provide fabric 502 of substrate 503. Weave 550schematically depicts the warp and weft of HFD weave pattern 556. TheHFD weave 550 is shown from three perspectives: swatch 553 in parallelto the view plane, representation 552, and representation 554. Therepresentations 552 and 554 correspond to sections through the weft/warparrangement of pattern 556, and are turned 90 degrees relative to swatch553. Representations 552 and 554 are parallel to the respectivesections/edges of swatch 553, and perpendicular to each other.Representations 552 and 554 enhance understanding of pattern 556relative to swatch 553 by showing an edge-on/thickness view of thewarp/weft arrangement, among other things.

In the middle part of FIG. 5B, herringbone weave 560 is depictedschematically—being comprised of fibers 501 to form fabric 502 ofsubstrate 503. Weave 560 has the warp/weft arrangement of a herringboneweave pattern 566. Herringbone weave 560 is shown from threeperspectives: swatch 563 parallel to the view plane, representation 562,and representation 564. The representations 562 and 564 correspond tosections through the weft/warp arrangement of fibers 501 at rightangles, and are turned 90 degrees relative to swatch 563.Representations 562 and 564 are parallel to corresponding edges ofswatch 563 and perpendicular to one another. Representations 562 and 564enhance understanding of pattern 566 relative to swatch 563 by showingan edge-on/thickness view of the warp/weft arrangement among otherthings. Typically, herringbone weave 560 is of the closed weave type.

The lower part of FIG. 5B schematically depicts 3/3 twilled weave 570which is one of a group of depicted twills 571 formed from fibers 501each to provide a corresponding fabric 502 of substrate 503. Weave 570schematically depicts the warp and weft of a 3/3 twilled weave pattern576 from three perspectives: swatch 573 parallel to the view plane,representation 572, and representation 574. The representations 572 and574 correspond to warp/weft sections through pattern 576, and are turned90 degrees relative to swatch 573 perpendicular to the view plane.Representations 572 and 574 are aligned parallel with the correspondingedges/sections of swatch 573, and perpendicular to one another.Representations 572 and 574 lend understanding of pattern 576 relativeto swatch 573 by showing an edge-on/thickness view of the warp/weftarrangement, among other things. The 3/3 twilled weave 570 is of aclosed type.

FIG. 5C shows three perspective visualizations of different weaves. Theperspective view of these weaves renders separate edge/sectionalrepresentations largely redundant. The upper part of FIG. 5C depictsanother of the twills 571, namely 2/2 twilled weave 576 a, which isformed from fibers 501 to provide fabric 502 of substrate 503. 2/2twilled weave 576 a includes swatch 576 b, edge 576 c, and edge 576 d,that collectively show weave pattern 576 e. Edges 576 c and 576 dprovide an edge-on/thickness view of swatch 576 b. It should be observedthat pattern 576 e is similar to pattern 576 (FIG. 5B, lower) except forthe number of warp or weft elements floated at one time. The 2/2 twilledweave 576 a is of a closed type. In the middle part of FIG. 5C, Dutchplain weave 577 a is shown that is formed of fibers 501 to providefabric 502 of substrate 503. Weave 577 a includes swatch 577 b, edge 577c, and edge 577 d, that collectively show weave pattern 577 e. Edges 577c and 577 d correspond to the edge-on/thickness view of swatch 577 b.Typically, weave 577 a is a closed weave type. In the lower part of FIG.5C, Dutch twilled weave 578 a is illustrated, which is formed fromfibers 501 to provide fabric 502 of substrate 503. Weave 578 a includesswatch 578 b, edge 578 c, and edge 578 d, that collectively show weavepattern 578 e. Edges 578 c and 578 d correspond to edge-on/thicknessviews of swatch 578 b. Typically, weave 578 a is a closed type.

FIG. 5D displays three more weave types of comparison 500 each comprisedof fibers 501 to provide fabric 502 and corresponding substrate 503. Theupper part of FIG. 5D depicts Leno weave 580 (a form of gauze weave)shown from two perspectives: swatch 581 in a plan view andrepresentation 582 turned 90 degrees and aligned parallel with thecorresponding edge of swatch 581. Swatch 581 and representation 582illustrate weft/warp constituents of pattern 580 a. Representation 582shows an edge-on/thickness view of the warp/weft arrangement of pattern580 a, among other things. Leno weave 580 is of the open weave type.

The middle part of FIG. 5D depicts Mock Leno weave 584 shown from threeperspectives: swatch 585 with length/width parallel to the view plane,representation 586, and representation 588 perpendicular torepresentation 586. The representations 586 and 588 correspond tosections through the weft/warp arrangement of weave pattern 584 a, areeach turned 90 degrees relative to swatch 585, and are each alignedparallel to the respective section/corresponding edge of swatch 585.Sectional representations 586 and 588 enhance understanding of pattern584 a by showing an edge-on/thickness view of the warp/weft arrangement,among other things.

The lower part of FIG. 5D depicts basket (panama) weave 590 shown fromthree perspectives: swatch 591 parallel to the view plane,representation 592, and representation 594. The representations 592 and594 correspond to sections/edges parallel to respective weft/warpaspects of pattern 590 a, are turned 90 degrees relative to swatch 591,and are perpendicular relative to one another. Representations 592 and594 enhance understanding of pattern 590 a relative to swatch 591 byshowing an edge-on/thickness view of the warp/weft arrangement amongother things.

Referring back to FIG. 4, the selected structure of the samplercore/substrate in operation 404 is further described. For instance,certain embodiments include a fabric of a woven type. In specificrefinements, the weave is one or more of: plain weave, satin weave,twilled weave, heddle weave, and herringbone weave. In further morespecific forms, the sampler incorporates a closed weave fabric core. Ineven more specific forms, a closed weave fabric core includes one orboth of a satin weave and a twilled weave. Still another even moreparticular form includes a closed harness satin weave. Yet a furtherparticular form employs a closed weave of the 4 HS type.

Considering also FIG. 6, a partially diagrammatic cross-sectional viewof sampler 100 is illustrated that corresponds to the section line 6-6shown in FIG. 1. In this sectional view, FIG. 6 illustrates structuralfabric core 606 of sampler 100; where like reference numerals refer tolike features previously described. Core 606 includes two opposingfunctionalized sublayers 604 each covered by a corresponding polymerlayer 602. Certain additional description of sublayers 604 and polymerlayers 602 is deferred until corresponding operations/conditionals408-420 of FIG. 4 are encountered in sequence hereinafter. Thickness T1of sampler 100 corresponds to double-headed arrow 106 inclusive of core606 and layers 602, and thickness T2 of sampler core 606 corresponds todouble-headed arrow 108 inclusive of core 606 without layers 602. Insome embodiments, the shape and volume of the sampler 100 inclusive oflayers 602, and core 606 can impact thermal behavior, samplerflexibility/rigidity, viability of analyte collection (like sufficiencyof collection surface area), and the like. Further, sampler dimensionsmay be constrained by other factors, such as instrumentation, durabilityand/or handling requirements. To provide a surface area suitable foranalyte collection in such embodiments, the dominant surface area(L×W—the “major surface area”) is along the side with the Length L andWidth W dimensions, where T1 and T2 are much less than L or W (T1<<L,T1<<W, T2<<L, T2<<W). For these embodiments, decreasing thicknesses T1,T2 decreases thermal mass for a given composition and fiber 501arrangement of core 606, such as its weave 516 for woven fabric 502 formof the core 606 (a specific type of substrate 503), which can enhancethermal desorption performance. However, a decrease in T1 generallypresents a trade-off—decreasing the degree of polymer 602 coverage ofcore 606, and correspondingly reducing sampler 100 stiffness and/orincreasing analyte affinity absent functionalization suitable toeffective analyte release/transfer; while a decrease in T2 presents atrade-off in terms of mechanical sufficiency potentially impacting wear,durability, and stiffness. As a result, in one form, the core 606 has athickness less than or equal to 0.5 mm (T2≤0.5 mm); in a more specificform, T2 is less than or equal to 0.3 mm (T2≤0.3 mm); in an even morespecific form, T2 is less than or equal to 0.12 mm (T2≤0.12 mm); and inan even more particular form, T2 is less than or equal to 0.1 mm (T2≤0.1mm). Given overall sampler thickness T1 remains larger than T2 withpolymer applied to the core 606 (T1>T2), one respective pairing with theT2 inequalities provides T1 less than or equal to 1 mm (T1≤1 mm) in oneform; in a more specific form, T1 is less than or equal to 0.8 mm(T1≤0.8 mm); in an even more specific form, T1 is less than or equal to0.5 mm (T1≤0.5 mm); and in an even more particular form, T1 is less thanor equal to 0.3 mm (T1≤0.3 mm).

Compositionally, natural fibrous materials include: wool, cashmere,alpaca, leather, cotton, silk, flax, hemp, tencel, jute, or the like;synthetic organic material includes: one or more synthetic organicthermoplastic or thermoset polymers, including polymeric nanotubes andnanofibers; inorganic material includes: glass, metal, metalloid,inorganic oxide, metal oxide coated fibers, ceramic, glass-ceramic, or acombination of these. Among the glass compositions, fibers may becomposed of pure silica (e.g., ASTROQUARTZ, JPS Composites Materials,Anderson, S.C., USA), or predominantly silica with inorganicconstituents to provide selected properties. For instance, suchsilica-based glass fibers may be selected from: HSG as previouslydefined herein, A-type glasses (e.g. alkali-lime glass with little or noboron oxide); E-type glasses (52%-56% silicon dioxide, 16%-25% CalciumOxide, 12%-16% Aluminum Oxide, 5%-10% Boron Oxide, 0%-2% Sodium Oxide &Potassium Oxide, 0%-5% Magnesium Oxide, 0.05%-0.4% Iron Oxide, 0%-0.8%Titanium Oxide, and 0%-1.0% Fluorides); E-CR-type glasses (e.g.,alumino-lime silicate with less than 1% wt alkali oxides with high acidresistance); C-type glasses (e.g., alkali-lime glass with high boronoxide content); D-glass (borosilicate glass with high dielectricconstant); R-glass (alumino silicate glass with no MgO or CaO); S-typeglasses (64%-66% Silicon Dioxide, 0%-0.3% Calcium Oxide, 24%-26%Aluminum Oxide, 0% Boron Oxide, 0%-0.3% Sodium Oxide & Potassium Oxide,9%-11% Magnesium Oxide, 0%-0.3% Iron Oxide, 0% Titanium Oxide, and 0%Fluorides—e.g., alumino silicate glass without CaO but with high MgO),and combinations of these various glasses—it being understood that theparenthetical descriptions of different glass types are exemplary onlyand any other formulas considered by those of ordinary skill in the artto be one of these glass types at the time of filing of the presentapplication are intended to be included.

Likely candidates for metal fibers include, but are not limited to,e.g., iron (Fe), aluminum (Al), copper (Cu), nickel (Ni), silver (Ag),and including metal alloys thereof. In a further refinement, in someembodiments metal fibers may be treated with acid or base to clean andactivate the surface of the fibers prior to use or subsequent processing(such as operation 414). In certain embodiments, metal fibers mayinclude a native oxide coating on the surface of the metal fibers.Fibers may be composed of or include, metal oxides, oxide-coated metals,or metals that include a metal oxide coating of the same or differentmetal provided that refractory properties of the metal oxide coating arecompatible with the underlying metal. Inorganic oxides encompass bothmetal oxides and non-metal oxides for fibers, including, but are notlimited to: Ag₂O, Al₂O₃, As₂O₃, As₄O₆, BaO, B₂O₃, BeO, Bi₂O₃, CO, CaO,CdO, CeO₂, CoO, CrO₃, Cr₂O₃, CuO, Cu₂O, Dy₂O₃, Er₂O₃, Eu₂O₃, FeO, Fe₂O₃,Ga₂O₃, GdO₃, GeO₂, Ho₂O₃, HfO₂, In₂O₃, IrO₂, K₂O, KNaO, La₂O₃, Li₂O,Lu₂O₃, MgO, MnO, MnO₂, Mn₂O₃, MoO₃, N₂O₅, Na₂O, Nb₂O₃, Nb₂O₅, Nd₂O₃,NiO, Ni₂O₃, PO₄, PbO, PdO, PmO₃, PrO₂, Pr₂O₃, PtO₂, Rb₂O, Re₂O₇, RhO₃,SO₃, SO₄, Sb₂O₃, Sb₂O₅, Sc₂O₃, SeO₂, SiO₂, Sm₂O₃, SnO₂, Ta₂O₅, Tb₂O₃,ThO₂, TiO₂, Tl₂O, Tm₂O₃, V₂O₅, WO₃, Y₂O₃, Yb₂O₃, ZnO, ZrO, ZrO₂, andcombinations of these various oxides. Other minor constituents commonlyfound in the subject material may also be found therein which areunlikely to influence the properties of the overall material including,e.g., alkali metal oxides, alkaline earth oxides, and impurities.

In certain embodiments, the sampler core, whether fibrous or otherwise,includes one or more of: glass, metal, metalloid, inorganic oxide,polymeric thermoplastic, polymeric thermoset, ceramic, glass-ceramic,and/or metal or glass coated with metal oxide as described furtherherein. In one specific embodiment of sampler 100, the core/substrateincludes one or more of: glass, metal, metalloid, inorganic oxide,ceramic, and glass-ceramic. In a more specific embodiment of sampler100, the core/substrate includes one or more of: HSG, metal, metalloid,metal oxide, ceramic, and glass-ceramic. In further more specificembodiment, the core is comprised of at least one of: HSG, metal,metalloid, and metal oxide. In an even more specific embodiment, thecore is comprised of one or more of: HSG, metal, carbon, and metaloxide. In still a more specific embodiment, the core is comprised ofHSG. In yet a more highly specific embodiment, the core is comprised ofS-glass. In still other specific embodiments, the core is comprised ofone or more glasses or metals coated with one or more compatible metaloxides. While S-glass is favored for some embodiments, it is surmisedother materials, such as those of the progressively more specificgroups/types listed above will perform similarly or even better incertain other embodiments.

Other considerations in the selection/performance of core compositionare intrinsic thermal properties, which relate to the ability torelease/transfer analyte(s) through thermal desorption when relevant, aswhen used with instrumentation 30, among other things. These propertiesinclude thermal conductivity and specific heat capacity. In certainembodiments, a fiber core has a thermal conductivity greater than about0.2 W/m-K. In further embodiments, the thermal conductivity is greaterthan about 0.4 W/m-K. In still other embodiments, the thermalconductivity is greater than about 0.6 W/m-K. Alternatively oradditionally, other embodiments have a specific heat of the fiber belowabout 1.3 J/g ° C. In further embodiments, the core fiber specific heatis in a range from about 1 J/g ° C. through about 1.3 J/g ° C.; yet inother embodiments, this specific heat is in a range from about 0.5 J/g °C. through about 1.2 J/g ° C.; and still other embodiments have a fiberspecific heat in a range from about 0.1 J/g ° C. through about 0.5 J/g °C.

Per FIG. 6, sampler 100 includes an analyte sampling surface 612 on eachopposing side of sampler 100, as defined by respective opposing polymerlayers 602. Layer 602 is disposed on fiber core 606 to collect, retain,transfer, and release trace particles and/or other forms of targetedcontraband or undesirable substance(s) for detection. In someembodiments, such detection may be performed with instrumentation 30through thermal desorption or in a different manner. Polymer layer 602may completely coat fiber core 606, or only partially cover/coat core606. In one form, the major surface area (L×W) on opposing sides ofsampler 100 are completely or partially configured with sampling surface612. In other embodiments, just a single side is completely or partiallyconfigured with a sampling surface 612. In a further instance a glove232 or finger cot 234 implementation of the sampler may only have asampling surface on its outer side, and/or may be confined to a selectedregion or regions thereof.

For the depicted embodiment, core 606 shown in FIG. 6 is comprised of afabric 502 with the 4 HS weave 516—both fabric 502 and weave 516 arefurther described in connection with FIG. 5A and accompanying texthereinbefore. Further, for the purposes of providing a fuller example inconnection with the conditionals/operations of process 400, fibers501/fabric 502 is made of S-glass. However, in other embodiments, themechanical and/or compositional aspects of the core/substrate mayvary—it being specific in this case just for the sake of example. TheFIG. 6 representation is shown with level, horizontal surfaces in blockform to preserve clarity of various features that may be readilyobscured or confused otherwise. However, core 606 comprised of fabric502/fibers 501 with 4 HS weave 516 would likely exhibit an undulatingcore surface 605 in a corresponding weave surface pattern—with greatercomplexity and unevenness (not shown). Correspondingly, polymer layer602 would tend to be uneven, too, depending somewhat on relativethickness and degree of coverage (not shown).

In addition, some fiber surfaces (such as glasses) can be tailored witha specified surface chemistry that may be useful to facilitate betterpolymer layer 602 coverage and/or provide a surface more compatible withselected analyte(s), and/or collection, retention, release, and transferto the extent fiber core 606 is uncovered by layer 602. The enhancedsurface chemistry may provide better surface homogeneity and moresuitable analyte affinity—directed to better analyte recovery whencompared with less homogeneous surface chemistry of other arrangements.Correspondingly, enhanced surface chemistry can enhance polymer coverageand/or the collection, release, transfer, and detection (i.e., signalintensity) of released analyte(s) with it.

By way of nonlimiting example, an S-glass/4 HS weave 516 form of sampler100 shall serve as the sampler core/substrate selected during operation404 of process 400 (FIG. 4) for nonlimiting illustrative purposes. Fromoperation 404, process 400 continues with conditional 405. Conditional405 tests whether the selected core/substrate material would benefitfrom a pre-treatment. If the test of conditional 405 is affirmative(Yes), process 400 proceeds to operation 406. If this test is negative(No), process 400 proceeds to conditional 408, bypassing operation 406.For this example, an effective pretreatment procedure is available soprocess 400 continues with operation 406. Typically pretreatment inoperation 406 removes contaminants, alters the material in some otherfashion, or otherwise prepares the material for subsequent operations.Accordingly, pretreatment may involve application of a chemical,thermal, and/or mechanical procedure. For the stated example, highlevels of nitrates are sometimes present in S-glass and potentially someother glass types, which is an unwanted contaminant. To remove thiscontaminant, a heat treatment is applied. It has been found exposure ofthe material to 500° C. for 4 hours or more is sufficient to reducenitrates to an acceptable level.

Other procedures additionally or alternatively may be applicable to thisexample material; and to different materials as might be performed underoperation 406 in other examples/embodiments. Under certain circumstancescommercially available glass or silica fiber materials are coated with avariety of chemicals such as binders, oils, resins, and other compoundsthat facilitate uses in a variety of industrial applications. Removal ofthese compounds is performed to enhance installation of specificcore/substrate surface chemistries at desired density in operation 414to be further described hereinafter. For example, untreated glass and/orsilica fibers can include many unavailable reactive surface sitesbecause these surface sites are physically obstructed by a surfacecoating or undesirable contaminants, or are chemically unavailablebecause of a previous reaction between adjacent silanols (e.g., metalhydroxyl groups) that form, e.g., bridging oxo groups. Furtherpretreatment information is deferred until operation 414 is reached byprocess 400.

From operation 406, process 400 advances to conditional 408, which testswhether a fill procedure should be performed. If the test is negative(No), process 400 continues with conditional 412, bypassing operation410. If the test is affirmative (Yes), process 400 advances to operation410. In operation 410, a particulate material is applied to core606/substrate 503 to enhance thermal and/or other desired properties assuited to the application. For the S-glass/4 HS weave example, operation410 is performed to at least partially fill the core 606 with alumina(Al₂O₃) nanoparticles to increase thermal performance because Al₂O₃ hasa thermal conductivity several times greater than S-glass. Thesenanoparticles are represented by small circles in sublayers 604 of core606 with only a few being designated by reference numeral 620 topreserve clarity. In FIG. 6, nanoparticles 620 are shown closer tosurface 605 in sublayers 604; however, they may become more deeplyembedded and uniformly dispersed than shown. In one embodiment, the meandiameter of nanoparticles 620 is about 50 nanometers (nm); but, in otherembodiments a differently sized nanoparticle, a larger particle, otherthan a nanoparticle, or nanoparticle may be used. Additionally oralternatively, one or more carbon-based allotropes can be used as anano-sized or other filling material that are selected for a desiredlevel of thermal conductivity/performance; such allotropes including:carbon nanotubes, graphene, amorphous carbon, carbyne (linear acetyleniccarbon), carbon nanofoam, fullerenes, glassy carbon, graphite, or thelike. In FIG. 6, nanoparticles 620 also represent nano-sized carbonallotrope forms to the extent otherwise designated. In yet anotherembodiment, the fill material is one or more of particles of: metaloxide, metalloid, metal, ceramic, and glass-ceramic. In a furtherembodiment, the fill material is comprised of particles of: metal oxide,carbon, ceramic, and glass-ceramic. In a more specific embodiment, thefill material is comprised of nanoparticles of metal, metal oxide and/orcarbon. In yet an even more specific embodiment, carbon nanoparticles ofa nanotube and/or graphene allotrope provide the fill material. In otherembodiments a different and/or multiple types of fill material may beused to coat, partially fill or generally completely fill thecore/substrate. Typically, fill material is selected to improve anaspect of the core 606 for which improvement is desired, such as athermal characteristic. In another form, particles of at least one ofmetal and metal oxide is used at least some of which may benanoparticles. In another form, the particles are alumina and are ofnanoparticle size. In other embodiments, operation 410 is not performedat all—such that no fill material is used, being bypassed by conditional408.

Next, process 400 encounters conditional 412, which tests whether tofunctionalize surface 605 of core 606 to provide sub-layers 604. If thetest is negative (No), procedure 400 continues with operation 416,bypassing operation 414. If the test is affirmative (Yes), process 400moves to operation 414. In operation 414, surface sub-layers 604 of core606 are formed to improve the desired collection and release of targetanalyte(s) with surface 605/sub-layer 604, improve subsequentapplication of polymer layer 602, and/or provide other desired featuresthrough installation of desired surface chemistry. In one form,functionalization may be performed according to the '910 patent, whichprovides exhaustive description thereof.

It has been discovered that a glass form of core 606 generally tends tobind with certain analytes to such an extent that release/transfer bythermal desorption can be hampered, resulting in a reduced detectionsignal. Moreover, glass surfaces tend to be polar which can affect theuniformity of polymer coverage in subsequent operations (such as polymerapplication in operation 416). Such nonuniformity also indirectly canimpact analyte collection and/or release because polymer 602 coverssurface 605 to a lesser/incomplete extent. Generally, polymer coating602 may not be uniform over surface 605 of core 606 due to 4 HS weaveshape or the like, so that functionalization facilitates a more robust,uniform analyte detection response. Fill particles (such as aluminananoparticles 620), can also tightly bind to analyte(s) and/or may alsobenefit from functionalization.

In FIG. 6, generic “R” functional groups are labeled in sublayers 604,where each “R” is appended to core 606 by a line representative ofbonding to core 606. The resulting interfacial sub-layer 604 isrepresentative of organo-silanes provided according to the '910 patentor other chemistry resulting from a different procedure. The relativesize of sub-layers 604 is not to scale in FIG. 6, and may in fact onlyhave a thickness of no more than about a molecule or so in someapplications. The '910 patent provides further details regarding variousfunctionalization operations/options, and is generallycompatible/adaptable with those of the present application. Toaccommodate functionalization, process 400 may include pre- andpost-treatments per the '910 patent to perform/enhance the formation ofsublayers 604 and further improve compatibility with subsequent stages.Some pretreatments may already have been described for operation 406 butare repeated here in connection with functionalization, namely: (a) toremove commercial coatings or surface contaminants (See '910 patent FIG.2a and accompanying text), an exemplary pretreatment process to preparefor functionalization of the core surface 605 is further discussed,which may be used as an addition or alternative to that previouslydescribed for operation 406; where such functionalization preparationpretreatment can activate and increase density of reactive groups suchas silanols on the surfaces of fibers 501 and/or correct unfavorablesurface chemistry—by way of example, fibers 501 treated with, e.g.,bases or acids can increase the density of silanols on the surfaces inthe absence of added water—while in others, hydrotreating the surfacewith an aqueous medium can increase the density of silanols or reactive(—OH containing) groups on surface 605; (b) silanizing fibers 501 bychemically attaching silanes (e.g., phenyl silanes) on surfaces 605 offibers 501, (c) conditioning (i.e., cleaning) surfaces 605 of thesurface-functionalized or modified fiber 501 fabric 502 material, and/or(d) post-treating the surface-modified fabric 502 to remove unreactedagents (or oligomerized but unattached silanes) from fabric 502.

FIG. 2b of the '910 patent shows an exemplary condensation reaction fordirect attachment of silane ligands or terminally functionalized silaneligands to activated anchor sites (e.g., silanols) on the surfaces offabric fibers that may be performed in operation 414. Surfaces 605including glass, metal oxide, and/or oxide coated glass or metal fibersare amenable to surface functionalization using a wide range offunctional groups through Si—O—Si bonds [or metal (M)-O—Si bonds in thecase of metal oxide and oxide-coated metal fibers] that form in concertwith Anchor groups (Z) attached to a silicon (Si) atom at the terminalattaching end of a Linking group (Y). Another terminal end of theLinking group (Y) may include other terminal groups (X), e.g., as shownin chemical expression [1] of the '910 patent.

In some embodiments, the silanization procedure of operation 414 mayinvolve chemically attaching silanes to reactive Si—OH groups on thesurface 605 of fibers 501 in sublayers 604. For example, Si—OH reactivesites on the surface 605 of the fibers 501 may attach to selected silaneligands via an Anchor group (Z) positioned at the attaching end of thesilane ligand. The reaction may form a Si—O—Si bond, e.g., via acondensation reaction. In some embodiments, silanes can attach directlyto reactive Si—OH (Anchor) groups (Z) in the absence of a Linking group(Y). FIG. 3 and accompanying text of the '910 patent provides furtherinformation.

Silane ligands suitable for selective collection of target analyte(s)include, but are not limited to, e.g., phenyl silanes; organosilanes;alkoxysilanes; alkyl silanes; siloxanes; phenyl-trimethoxysilanes;silanols; combinations of these various silanes; and/or hydrocarbylderivatives thereof. As described further in the '910 patent,functionalization/passivation of any residual reaction sites can yieldfurther improvements in surface chemistry results and/orfunctionalization processing may be performed multiple times per the'910 patent. Phenyl silanes represent an exemplary surface chemistry formodification and functionalization of glass, silica, metal oxide, and/oroxide-coated glass or metal fibers 501 within the sampling fabric 502 ofcore 606 for collection of a wide variety of organics. Phenyl silanesprovide a thermally robust and thermally stable surface chemistry attemperatures in excess of 400° C. In addition, phenyl silanes canprovide a lipophilic surface with a general affinity for various organicmaterials, and additionally, greater chemical selectivity for TNT andother nitroaromatics, as detailed further in the '910 patent. Withterminal groups attached to the silanes, various other terminal groupsor ligands can be chemically attached to the terminal end of the silaneligands to provide enhanced affinity/selectivity. Once silanization iscomplete in operation 414, sampling surface 605 may be further treatedto ensure that silanes are completely bound to the surface and to removeunwanted reactants and side products. This stabilization processprepares the functionalized surface for collection of target analytes.In other embodiments, a surface chemistry functionalization based onsomething other than silanization may be used. For such embodiments,operation 414 includes appropriate stabilization treatment, asapplicable.

The schematic view of FIG. 7, depicts a portion of alternative sampler800 in perspective. Various features of sampler 800 are not shownrelative to scale to highlight certain aspects and does not includecomplete crosshatching to avoid obscuring certain features. Phenylterminal functional group P of sampler 800 is a specific implementationof operation 414, with only some being specifically designated by thereference characters to preserve clarity. In other words, phenyl groupsP are a specific form of the generic silanization terminal groups Rshown in FIG. 6. Double polymer layering 602, 802 is applied over phenylgroups P. Outer/upper surface 802 defines sampling surface 802. Sampler800 does not specify any particular weave unlike weave 516 of sampler100.

Returning for FIGS. 4 and 6, from operation 414 process 400 advances tooperation 416. In operation 416 polymer layer 602 is formed on core 606that defines sampling surface 612. Polymer layer 602 may be applied tocore 606 by various means, including without limitation: an aqueous orother liquid-based dispersion of polymer particles in the form of apainted or brushed-on coating, a spray, dipping in the liquid, or thelike; a powder of polymer particles deposited on the core; molding apolymer film, sheet, or lamination onto the core, or such otherapplication as known to those of ordinary skill in the art. The amountof polymer applied is typically in a range of about 2% wt through about50% wt depending on various target properties of sampler 100 such asstiffness, analyte collection/release, the degree of core coverage bythe polymer, sampler thickness/thermal mass, and the like—as discussedfurther hereinafter. Indeed, in some embodiments, only partial corecoverage by the polymer may be desired.

As to composition, one preferred embodiment of the polymer layer 602,802 is comprised of one or more of: polymeric organofluorine, polyamide,polyimide, PolyBenzImidazole (PBI), PolyDiMethylSiloxane (PDMS),sulfonated tetrafluoroethylene (PFSA), and Poly(2,6-diPhenyl-p-PhenyleneOxide) (PPPO). PPPO is also known by the trademark TENAX TA, and aPPPO/graphitized carbon combination (also known by the trademark TENAXGR) is included in the group because PPPO is a constituent of both theabove group listing and the graphitized carbon combination.Alternatively or additionally, in other forms the composition of thepolymer applied to any of the previously described cores may be a memberof any of the following successively more specific listings (a)-(e): (a)perfluorocarbon, perfluoroether, Ethylene-TetraFluoroEthylene copolymer(ETFE), Ethylene ChloroTriFluoroEthylene copolymer (ECTFE),poly(tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride) (THV)copolymer, PolyVinylidene diFluoride (PVdF), FluorinatedEthylene-propylene (FEP), PolyChloroTriFluoroEthylene (PCTFE), PolyVinylFluoride (PVF), PolyTRiFluoroEthylene (PTRFE),poly(vinylidene-tetrafluoroethylene) copolymer,poly(vinylidene-trifluroethylene) copolymer, PPBI, PDMS, and PPPO; (b)perfluorocarbon, perfluoroether, ETFE, FEP, THV copolymer, PVdF, andPPPO; (c) perfluorocarbon, PerFluoroAlkoxy (PFA), ETFE, PVdF, and FEP(where “pefluoroether” is inclusive of PFA); (d) PFA, ETFE, FEP, andPTFE; and (e) PTFE. While PTFE is favored for certain embodiments, it issurmised that analog polymers and others like PTFE will performsimilarly. Also, to the extent thermal desorption is used with thesampler 100, 800 it is a preference that polymer 602, 802 have a thermaldecomposition temperature above the temperature applied to performthermal desorption with detection instrumentation 30.

Accordingly, one specific form of the sampler 100 applies PTFE to theexemplary S-glass/4 HS weave core. In one approach, PTFE is applied toS-glass fibers by depositing a coating on the core of an aqueousdispersion of PTFE polymer particles. This deposition may includebrushing the dispersion on the core, dipping the core in the dispersion,or the like. In further embodiments, a different polymer may be appliedand/or a different manner of application used. Additionally oralternatively, in other embodiments the core differs in compositionand/or arrangement of core fibers. Such arrangement can differ amongvarious embodiments as to type: non-fibrous nonfabric, nonwoven fabric,and/or woven fabric; and if the core includes a woven fabric, the weavetype of such fabric can include or vary from the 4 HS type, and may havea closed or open weave for different embodiments.

Per FIG. 4, process 400 moves from operation 416 to operation 418. Inoperation 418, the polymer application is cured/heat-treated as neededfor the core/polymer materials utilized to prepare sampler 100, 800 foruse with detection instrumentation. In one embodiment, heat treatment isperformed for the aqueous dispersion form of PTFE applied to anS-glass/4 HS woven fabric sampler core. It has been discovered that heattreatment in the range between the polymer melting point and the thermaldecomposition temperature tends to yield a better detection responsecompared to heat treatment temperatures outside of this range, andfurther has been surprisingly found to be a factor in controllingsampler stiffness. In one form, operation 418 heats a glass core with aPTFE polymer core application to a temperature of about 400° C. for 30minutes; where the PTFE melting point is about 327° C. and the thermaldecomposition temperature is about 448° C. In an alternative form, theapplied temperature is about 425° C. for 30 minutes. In a furtherembodiment, the heat treatment temperature is between about 390° C. andabout 435° C. and applied for at least 30 minutes. In other embodiments,a different cure/heat treatment may be applied after polymer applicationthat may further include control of applied pressure/vacuum. In stillother embodiments, a different core and/or polymer application is usedwith an appropriate heat treatment, if any.

In addition to heat treatment of operation 418, another factor impactingsampler stiffness and signal response is the relative amount of polymerapplied to the core 606. After curing in operation 418, the calcinedamount of the polymer applied is broadly in the range from about 2% wtthrough about 50% wt. In one form, the calcined polymer amount aftercuring is less than or equal to about 40% wt. For a further form, thecalcined polymer amount after curing is less than or equal to about 20%wt. In still another form, the calcined polymer amount after curing isin a range from about 20% wt through about 40% wt. Still a differentform has a calcined polymer amount in a range of about 24% wt throughabout 36% wt.

With the addition of polymer layer 602 for sampler 100 (and potentiallylayer 802 of sampler 800), thickness T1 of sampler 100 (or sampler 800)is established, which can have a bearing on thermal behavior andaccordingly the release of analyte(s) through thermal desorption withinstrumentation 30—much like thickness T2 of core 606. One preferredembodiment based on a nominal core thickness T2 of about 0.3 mm has anoverall sampler thickness T1 of less than or equal to about 0.8 mmdepending on polymer amount applied. In another embodiment, the T2thickness is less than or equal to about 0.5 mm. In still anotherembodiment, sampler thickness T2 is less than or equal to about 0.12 mm.

From operation 418, process 400 continues with conditional 420.Conditional 420 tests whether to apply a further coat of polymer. Suchpolymer may be the same or different from that applied previously. Ifthe test is negative (No), process 400 continues with conditional 422.If the test is affirmative (Yes), process 400 loops back to operation416 to apply further polymer of the same type or a different type. Itshould be understood, that with multiple applications of polymer(s),operation 418 may be performed for each layer separately or may bedeferred until some or all of the polymer/polymers is/are applieddepending on the nature of the polymer(s), the application regime inoperation 416, and curing technique(s) in operation 418.

After looping back to operation 416 for further polymer application, inone multilayer polymer embodiment, at least two or more thin PTFEapplications occur. Such duplicative applications may be individuallythinner than would the application of just one thicker polymer layer. Inanother embodiment, a two-layer polymer has an inner layer of PTFE andan outer layer of PPPO. In still another two-layer polymer embodiment,an outer layer of TENAX GR (PPPO/graphitized carbon combination) isapplied on an inner layer of PTFE. In FIG. 7, as previously indicatedsampler 800 includes two distinct polymer layers 602 and 802 that may beof the same or different compositions depending on amount and relativecoverage. The outer polymer layer 802 defines sampling surface 812 thatoperates in a manner analogous to sampling surface 612, which is showncovered by polymer layer 802 in FIG. 7. Polymer layer 602 serves as aninner, base layer relative to outer layer 802. In accordance withprocess 400, additional polymer applications may take place aspractically limited by performance requirements or the like; while inother embodiments, no more than the first polymer layer 602 applicationtakes place.

Flexure of the sampler or conversely “stiffness” may be empiricallyevaluated by determining flexural modulus of the sampler as definedherein. The flexural modulus is similar in some respects to the morefamiliar Young's modulus, both are often similar in value for a givenmaterial with common units of measure (units of pressure) but each isdetermined differently. Flexural modulus is commonly used with syntheticorganic polymers and composites thereof. In certain embodiments, asampler has a flexural modulus greater than or equal to about 0.75GigaPascal (GPa). In still further embodiments, the flexural modulus ofthe sampler is greater than or equal to about 1.0 GPa. In differentembodiments, the flexural modulus of the sampler is less than or equalto about 2.0 GPa. In still other embodiments, the flexural modulus ofthe sampler is less than or equal to about 3.0 GPa. In still furtherembodiments, the flexural modulus is less than or equal to about 4.0GPa. For some preferred embodiments, the sampler flexural modulus is ina range of about 0.75 GPa through about 10 GPa. In some more preferredembodiments, the sampler flexural modulus is in a range from about 1 GPathrough about 8 GPa. In some even more preferred embodiments, theflexural modulus is in a range from about 2 GPa through about 6 GPa.

When conditional 420 is negative, whether following just one polymerapplication or multiple polymer applications, conditional 422 isencountered. Conditional 422 tests whether more sampler material is tobe made. If the answer to this test is affirmative, process 400 loopsback to operation 404 to perform the previously described conditionalsand operations to the extent applicable—eventually returning toconditional 422 to test for continuation again. If the answer to thetest of conditional 422 is negative (No), then process 400 halts. Thesampler material resulting from process 400 is shaped as desired usingstamping, etching, trimming, cutting, or another procedure to providesampler 100 with the desired shape. In some embodiments, sampler 100 hasa sampling surface with a shape/perimeter selected from: a circle, anoval, an ellipsis, a rectangle, a square, a triangle, a regular polygon,an irregular polygon, a polyline, or combinations thereof. In certainembodiments, shaping may take place before provision in operation 404 orelsewhere during process 400 before conditional 422 is encountered. Tothe extent desired, sampler 100 may be cleaned and dressed after process400 and optionally packaged prior to use. In still other embodiments,the sampling surface takes the form of a finger cot 234, glove 232, or aportion thereof; or the sampler may be selectively attachable to thefinger cot 234 or glove 232 (See kit 200 of FIG. 2).

FIG. 8 is a flowchart describing process 700 directed to the use ofsampler 100 or 800; where previously described reference numerals referto like features. Process 700 begins in stage 702 to start sampler 100,800 application. From stage 702, process 700 advances to conditional 704to test if the application is for trace analyte detection or anotherapplication. If the test is negative (No), process 700 bypasses severalstages to next encounter conditional 716 as described furtherhereinafter. If the test is affirmative (Yes) for conditional 704,operation 706 is encountered in which the test article 50 is identifiedor otherwise predefined or known in advance, and sampler 100, 800 isapplied to collect analyte(s) from surface 54 of test article 50 inaccordance with any of the approaches described in connection with FIGS.1-3—that is using sampler 100, 800 to collect one or more targetanalytes by swiping, wiping, suction, with a wand, or the like, and/orthrough an analyte-entrained airflow—as could be employed withpass-through portals (See the '513 patent) to name a few examples. Testarticle 50 may be in any of a number of different forms, such ascargo/freight, associated packaging, shipping canisters or containers,tanks, crates, boxes, luggage, barrels, packing cases, child car seats,strollers, wheelchairs, purses, briefcases, travel cases, books andother documents, backpacks, electronic equipment (like laptops, tablets,headphones/ear buds, Personal Digital Assistants (PDA), and/or cellularphones), clothing/apparel/accoutrements, skin surfaces, vehicles,countertops, floors, walls, ceilings, and/or other surfaces as may occurto an operator.

Once analyte collection is completed with sampler 100, 800; transfer ofthe collected analyte(s) to appropriate trace detection instrumentation30 is next performed in operation 708. In operation 708, such transfertypically involves a controlled release of the analyte(s) from sampler100, 800. Such release may be performed chemically using appropriateagents/solutions and or agitation (such as stirring, churning, rocking,shaking, swaying, teetering, quavering, rolling, wobbling, oscillating,vibration, mixing, scrubbing, scouring, or other physical disturbance)with subsequent transfer to instrumentation 30, or through thermaldesorption to release analyte(s) for processing by detector 32 whilesampler 100, 800 is at least partially inserted in slot 40—to name a fewexamples. Further, application of more than one liquid may be used toclean/extract analyte(s) from sampler 100, 800; utilization of an acid(such nitric acid), a base (such as sodium hydroxide), water, or one ormore organic solvents; and/or a mixture of a oxidizer (like a peroxidesuch as hydrogen peroxide) with a source of one or both of onium andcarbonate. In some embodiments, the surface of the swipe sampler fabricretains the analyte(s) until thermally released into instrumentation 30at a release temperature greater than the collection temperature thatmay involve certain detection instrumentation gas flow(s) of controlledflow rate(s), composition(s), and temperature(s). In certainembodiments, the release includes thermally desorbing the analyte(s) ata temperature between about 100° C. and about 500° C. In preferredembodiments, the analyte release temperature is less than any thermaldecomposition temperature associated with sampler 100, 800. For instancea thermal desorption temperature equal to or less than 450° C. has beenfound suitable for PTFE-coated S-glass samplers to provide just onenonlimiting example. Once transferred, in operation 708 analyte(s) areevaluated by instrumentation 30 to determine if one or more targetanalytes are present, the results may be provided via display 34 and/orprinter 38 for the configuration previously described in connection withFIG. 1. The '910 patent further describes analyte sampler removaltechniques in connection with TABLE 6.

From operation 708, process 700 continues with operation 710. Inoperation 710, sampler 100, 800 is prepared for re-use. The analyterelease/transfer to instrumentation 30 may self-clean/prepare sampler100, 800 for reuse. In the case of thermal desorption, the desorptiontemperature may be sufficient to self-clean/prepare sampler 100, 800 forreuse, or may be capable to subjecting sampler 100, 800 to an elevatedtemperature/time period sufficient to prepare for reuse. In otherembodiments, the release of analyte(s) includes mechanically and/orchemically cleaning the surface of the sampler 100, 800 to prepare forreuse or collection of other analyte(s) from a selected surface. Instill other embodiments, a completely separate treatment is performed toplace sampler 100, 800 in condition for reuse under operation 710. Fromoperation 710, process 700 advances to conditional 714, which testswhether to perform another trace detection, and may include reuse ofsampler 100 after preparation in operation 710. If the test isaffirmative (Yes), process 700 loops back to repeat operations 706, 708,710, and conditional 714. If the test is negative (No), process 700falls through to conditional 716, which is also reached directly from anegative result of the test of conditional 704.

Conditional 716 tests whether sampler 100 is of a type suitable fordetection of an actinide series member, such as uranium, and whether totest for the same. It should be appreciated that samplers suitable foruse in earlier operations to detect non-nuclear analyte(s) may or maynot be preferred for nuclear material detection. If the test result isnegative (No), process 700 moves forward to conditional 720, and if thetest result is affirmative (Yes), process 700 moves to operation 718. Aprincipal technique employed by the International Atomic EnergyAuthority (IAEA) for the enforcement of the Non-Proliferation of NuclearWeapons Treaty (NPT) involves the use of environmental sampling todetect nuclear signatures that might reveal improper activities atotherwise declared facilities. Nuclear processing activities can leavetrace signatures on surroundings that may be sampled by collecting dust.Uranium is often found in the form of U₃O₈ or UO₂, which are crystallinecompounds with relatively low solubility in water. Because U₃O₈ is oneof the most stable forms of uranium, it is commonly found in nature.UO₂, on the other hand, is typically the uranium chemical form of choicein the final stages of nuclear fuel fabrication. Uranium Ore Concentrate(UOC) or “yellow cake,” as it is commonly known, is characteristically acommercial product of a uranium mill, usually containing a highconcentration (at least 90%) of uranium oxide U₃O₈. Uranyl fluoride(UO₂F₂) is a decomposition product that forms from the reaction ofmoisture and uranium hexafluoride (UF₆). Another compound sometimesfound in such samples is uranyl nitrate (UO₂(NO₃)₂), which is preparedfrom uranium salts treated with nitric acid. Uranyl nitrate is acompound sometimes encountered in the reprocessing of spent fuel. Inaddition, still another uranium compound that might be encountered isuranyl orthophosphate (UO₂(HPO₄)*4H₂O) that is also known by theabbreviation “HUP.” Standard sampling procedures normally smear highlyclean pieces of cotton fabric across surfaces of interest to collect adust sample that is later subjected to in-depth analysis. Among thedrawbacks of the existing scheme is the need for complete chemicaldigestion of the cotton/dust sample matrix, which is often timeconsuming/labor intensive, limiting laboratory throughput, elevatingcosts, and adding to background contamination from the sampling fabric,which ultimately limit test sensitivity.

In contrast, it has been surprisingly discovered that certainpolymer-coated cores or substrates provide high collection efficiency ofindustrial dust, including uranium compound particles of particularinterest for nuclear inspection protocols. In addition to nuclearsafeguard applications, this technique has application to the safety andsecurity monitoring of nuclear power reactors and related facilities.Accordingly, in operation 718, testing with sampler 100 is performed forthe trace detection of uranium. During operation 718, the collectedsurface-bound particles can be readily removed (extracted) by liquidfrom the polymer-coating, which may be performed more quickly and withless labor than pre-existing schemes relying on cotton fabriccollectors. Extraction may or may not involve digestion of some or allof the PTFE-coated sampler because release of certain uraniumcompound(s) from PTFE can be accomplished without complete digestiondepending on the applicable conditions—such as the extraction liquidcomposition, length of exposure to the extraction liquid, and theparticular uranium compound(s) being sought for release. It is surmisedthat PTFE analogues/homologues and other similar polymers other thanPTFE will perform suitably or even better than PTFE for certain corecompositions, analytes, coating combinations, sampler applications, orthe like.

In regard to the extraction liquid composition, it has been discoveredthat at least to some extent, the degree of extraction depends on theuranium compound(s) being sought for removal, the relative amount ofsuch compound(s) captured with the sampler, and the strength of one ormore active agents of the extraction liquid. For certain preferredembodiments, the extraction liquid includes an organic solvent. Certainembodiments include an acid in the extraction liquid; some more specificembodiments include the acid as a mineral acid type in aqueous solution;and even more specific embodiments include the acid as nitric acid(HNO₃) in aqueous solution. While yet other embodiments of theextraction liquid include a base, some specific embodiments include thebase as an alkaline agent in aqueous solution, and even more specificembodiments of the extraction liquid include sodium carbonate (Na₂CO₃)as the base in aqueous solution. Still other embodiments of theextraction liquid include a mixture of an oxidizer and one or both ofonium and carbonate, while in still more specific embodiments themixture includes an oxidizer in the form of a peroxide and includes oneor more of onium and carbonate, and an even more specific embodimentincludes the oxidizer in the form of a hydrogen peroxide, and ammoniumcarbonate. See Experimental Examples Eleven and Twelve for more detailsregarding uranium detection and related analysis.

It has further been surprisingly discovered that the background uraniumpresent in the sampler can be reduced with certain applications of aPTFE coating. It is surmised that PTFE analogues/homologues and othersimilar polymers other than PTFE will perform suitably or even betterthan PTFE for certain core compositions, analytes, coating combinations,sampler applications, or the like. One embodiment for preparing thesampler includes depositing PTFE nanoparticles from a colloidalsuspension on a glass fiber core by dipping in or painting on thesuspension liquid. Another embodiment for preparing the sampler includesplacing the PTFE-coated sampler in a liquid agent to reduce uraniumcontent of the PTFE and/or reduce impurities. Yet another embodiment forpreparing the sampler includes applying an acid form of the liquid agentin aqueous solution to the PTFE-coated sampler to reduce backgrounduranium content of the PTFE and/or reduce impurities. An even morespecific embodiment for preparing the sampler to reduce uranium contentof the PTFE and/or reduce impurities includes applying an oxidizer andone or both of onium and carbonate; and a still more specific embodimentincludes peroxide in this oxidizer; and yet an even more specificembodiment includes hydrogen peroxide in the oxidizer and ammoniumcarbonate. In still other embodiments for the sampler apparatus, theuranium background is less than or equal to 10 ng/g (10 nanograms (ng)of uranium per sampler gram (g)). In more specific embodiments, theuranium background of the sampler is less than or equal to 1.0 ng/g. Ineven more specific embodiments, the uranium background of the sampler isless than or equal to 0.1 ng/g. In still even more specific embodiments,the uranium background of the sampler is less than or equal to 0.010ng/g. See Experimental Example Thirteen for more details regardingbackground uranium reduction and related analysis.

From operation 718, process 700 continues with conditional 720.Conditional 720 tests whether to apply a sampler to test for heavymetals in certain industrial settings. If the test result is negative(No), process 700 falls through to conditional 724. If the test resultis affirmative (Yes), process 700 advances to operation 722. Inoperation 722, a PTFE-coated core sampler or similar arrangement will beswiped on selective surfaces to pick up dust in an industrial settingsuch as a mine or metal processing plant, where metal-based content willpotentially be collected. Next, under operation 722, digestion andcomplimentary chemical testing will be performed to determine the degreeto which a worker will be exposed to certain heavy metals. Fromoperation 722, process 700 moves to conditional 724. Conditional 724tests if sampler application(s) should be continued. If the test resultis affirmative (Yes), process 700 returns to conditional 704 to repeatit and potentially any of operations/conditionals in the range from706-722 as appropriate. If the test result is negative (No), process 700halts in stage 726, stopping further sampler applications. There aremany different potential contraband or undesirable substances(previously defined) that may be a target analyte for sampler 100.Alternatively, any contraband or undesirable substance not listedtherein may be a target of sampler 100 and instrumentation 30.Alternatively or additionally, in further embodiments any non-contrabandsubstance and/or a desired substance may be a target for detection withsampler 100 and instrumentation 30. In yet other embodiments, thesubstance targeted for detection may be one or more of contraband,non-contraband, undesirable, desirable, or a still different substanceof interest.

Samplers (such as sampler 100) have been described in terms of severaldifferent innovative mechanical, structural, thermal, and/orcompositional/material features, elements, characteristics, properties,and parameters; however, dimensioning, relative or absolute—especiallythree-dimensional (3-D) qualities has not been a major focus—given thatsampler 100 has largely been portrayed as a flat-type with L and W muchlarger than thickness (L, W>>T1, T2) thus far. Previously, sampler shapehas been depicted as being a planar pad, swipe, or strip type such asthat shown in FIGS. 1-3. Indeed, as shown in these figures, the samplersappear as two-dimensional planar rectangles with little or effectivelyno third dimension; however, as a solid object it should be generallyunderstood a working sampler implementation also has a third dimension,although it may be somewhat negligible compared to its other dimensions.Among the embodiments of such planar samplers is one with qualitativestiffness/bending resistance in a range from that of polymer-coated 20lb. weight print paper through polymer-coated cardstock, or that of apolymer-coated fabric; and to have comparable elastic resilience to“spring-back” or otherwise return to its original planar for—or at leastsubstantially. However, different dimensional, stiffness, and/orelasticity properties are provided in other sampler embodiments, and itshould be appreciated that the various sampler embodiments are notlimited to the depictions and accompanying exemplary descriptionsprovided herein in connection with FIGS. 1-3 or otherwise.

Widely used lineal dimension descriptors include length, width, depth,breadth, height, and thickness, but are sometimes used ambiguously, canvary in preferred use from one field to the next, and may be especiallycontext sensitive. To promote a common understanding, three lineal/axialdimensions that are orthogonal to one another (rectangular) aredesignated for the purpose of describing three-dimensional (3-D) aspectsof samplers: length (L) as the largest dimension, height (H) as thesmallest dimension, and width (W) as the intermediate dimension. HeightH was selected in lieu of thickness to avoid confusion with previouslydescribed thicknesses T1 and T2—understanding they all correspond to thesmallest dimension. It should be understood that L and W may beapproximately equal to each other (L≈W), W and H may be approximatelyequal to each other (W≈H), and L, W, and H may be approximately equal toeach other (L≈W≈H)—thus the general case is described by the inequalityexpression: L≥W≥H. Indeed, in the case of an ideal right cylindricalembodiment, two of the three dimensions would be equal to each other.Accordingly, as used herein, L, W, and H are oriented in such a mannerthat as each axis extends along the object being measured the inequalityexpression L≥W≥H is obeyed. Under this measurement procedure, theabsolute longest dimension need not be designated by L as long as Lalong the object is longer than W, W along the object is longer than Halong the object, and L, W, and H are orthogonal. This corresponds tothe usual way a rectangular parallelepiped (rectangular solid) would bemeasured along its outer edges rather than using the absolute longestlength, which is the diagonal. For many planar samplers corresponding tothe type represented in FIGS. 1-3, the height dimension H may beconsiderably less than a tenth ( 1/10th) of the width dimension W—suchthat width W varies from height H by one order of magnitude or more.Under certain circumstances/applications, samplers so dimensioned (H<<Wby at least an order of magnitude) can be considered approximatelytwo-dimensional, similar to those illustrated in FIGS. 1-3.

It has also been discovered a generally nonplanar form of sampler may bedesirable under certain circumstances that has height H generally closerto width W than for the planar type, and either or both of height H andwidth W are comparable to length L. This dimensioning corresponds to athree-dimensional (3-D) sampler type that is more perspectival thangenerally flat, planar samplers with H<<W. Initially referring to FIG.24, one type of three-dimensional substance sampler 1000 (alternativelydesignated collector 1002) is illustrated in the form of substancecollection framework 1010. Length L of framework 1010 is represented bythe vertical juxtaposed line segment (axis) designated by referencenumeral 1012 and the width W of framework 1010 is represented by thehorizontal juxtaposed line segment (axis) designated by referencenumeral 1014, which are perpendicular to each other and parallel to orcoplanar with the view plane of FIG. 24. The height H extends along anaxis perpendicular to the view plane of FIG. 24 and is represented bythe concentrically arranged circle and cross hairs designated byreference numeral 1006. In one form, L, W, and H of three-dimensionalsampler 1000 are all dimensionally within the same order of magnitude.In one embodiment of sampler 1000, H is one-eighth (⅛) or more of W andW is at least five-eighths (⅝) of L. In a more preferred embodiment ofsampler 1000, H is three-fourths (¾) or more of W and/or W is at leastthree-fourths (¾) of L. In an even more specific embodiment of sampler1000, H is one-half (½) or more of W and W is at least seven-eighths (⅞)of L. In another even more favored embodiment of sampler 1000, none ofL, W, and H are more than 1.5 greater than another. In still a morefavored embodiment of sampler 1000, none of L, W, and H are more than1.25 greater than another.

In addition to the dimensional features, various mechanical, structural,thermal, and compositional/material features of sampler 1000 shall bedescribed in connection with FIGS. 24 & 25. However, beforehand FIGS. 22& 23 are described to better elucidate the complex three-dimensionalpattern of framework 1010 shown in FIGS. 24 & 25. By way ofintroduction, FIG. 22 provides a description of the fundamentalmechanical/structural constituent 1005 that corresponds to ageometrically pattern repeated in a coincident fashion to buildhoneycomb 1030 of FIG. 23. The edges and adjoining vertices of thishoneycomb corresponds to the framework 1010 of FIG. 24. In FIG. 23,solid coincident blocks 1034, each are diagrammatically representativeof the shape outlined by mechanical/structural constituent 1005, fittogether to provide a solid geometry honeycomb 1030 structure used tobetter explain and visualize the role of its features in the subjectsampler 1000 of FIGS. 24 and 25. From the description of the FIG. 23honeycomb 1030, it transitions to the more complexcage/reticular/lattice-like embodiment of collection framework 1010 ofFIG. 24 and further assists in explaining various attendant embodiments.From there, the cross-sectioned framework portion 1080 of FIG. 25 isdescribed to further explain and visualize sampler 1000. FIGS. 24 & 25conclude by describing various sampler 1000 representative applicationsand alternative embodiments thereof.

With this summary of FIGS. 22-25 in mind, FIG. 22 is considered next ingreater detail. Turning then to FIG. 22, a diagrammatic perspective viewof a convex polyhedron in the form of a dodecahedral, truncatedoctahedron 1008 represented by schematic wireframe structural pattern1013 is illustrated, with mechanical/structural constituent 1005corresponding to the illustrated shape; where like reference numeralsrefer to like features previously described. Truncated octahedron 1008defines thirty-six (36) edges 1013 a joined together by twenty-four (24)vertices 1013 b (a truncated octahedron is equivalently a bitruncatedcube). Structural constituent 1005 is provided in the form of aschematically illustrated truncated octahedron framework 1015. Framework1015 is based on wireframe pattern 1013, which corresponds to edges 1013a and vertices 1013 b of the truncated octahedron 1008. In pattern 1013,the arrangement of edges 1013 a and vertices 1013 b define twelve (12)open faces 1017 that correspondingly have twelve (12) facialopenings/apertures 1018 that open external to framework 1015 andconstituent 1005. Six (6) open faces 1017 are approximately regular,geometrically coincident hexagons 1020, and the remaining six (6) openfaces 1017 are approximate, geometrically coincident rectangles 1022(approximately squares). Furthermore, framework 1015 internally definesa like-shaped chamber 1019. Chamber 1019 intersects the twelve (12) openfaces 1017 and corresponding facial openings 1018. Only a few of edges1013 a, vertices 1013 b, faces 1017, openings 1018, hexagons 1020, andrectangles 1022 are designated by reference numerals to preserveclarity.

Correspondingly, truncated octahedron framework 1015 is comprised oflink/bar members 1024 each corresponding to a different edge 1013 a. Barmembers 1024 are each elongate, and generally straight with one bar end1026 positioned opposite another bar end 1026. Three bar ends 1026 cometogether at a corresponding node/vertex 1013 b to form a nodal joint1028. The three joined bar members 1024 extend away from joint 1028 incorrespondence to the respective edges 1013 a. Collectively, thirty-six(36) bar members 1024 and twenty-four (24) joints 1028 define framework1015, which is also a form of truncated octahedral cage 1021. Barmembers 1024 and joints 1028 may be integral to one another, consistingof a single piece of material. Such construction can be performed bymechanical or laser machining, etching, or the like of a unitary pieceof material, such as a metal, ceramic, or metalloid. Alternatively, barmembers 1024 may be fastened together with mechanical fasteners, bywelding, brazing or soldering, by chemical medium/media such asadhesive(s), a 3-D printing technique, or the like. In still otherembodiments, a combination of these approaches may be utilized. Only afew of bar members 1024, bar ends 1026, and joints 1028 are designatedby reference numeral to preserve clarity. It should further be notedthat members 1024 may be coated with a polymer such as that previouslydescribed in connection with sampler 100.

Additionally referring to FIG. 23, a diagrammatic, perspective view of a3-D bitruncated cubic honeycomb 1030 is illustrated that is comprised ofgeometrically coincident truncated octahedra 1008; where like referencenumerals refer to like features previously described. Honeycomb 1030 isalso called a truncated octahedrille and is more generally a form oftessellation 1032. Honeycomb 1030 is of a solid geometric form tofunction as a visualization aide to conceptually bridge understandingfrom constituent 1005/framework 1015 (FIG. 22) and truncated octahedron1008 (FIGS. 22 & 23), to framework 1010 (FIGS. 24 & 25). Accordingly,solid truncated octahedral “blocks” 1034 are geometrically solidpolyhedrons shown with appropriate shading to illustrate thenature/shape of the honeycomb 1030. It should be appreciated that theshaping and sizing of blocks 1034 renders them approximately coincidentrelative to one another. As a result, blocks 1034 approximately, if notexactly, occupy the same space if overlapping one another. Blocks 1034fit together congruently, arranged and shaped in a complementaryorientation such that edges 1013 a and vertices 1013 b of octahedra 1008abutting one another can be merged or united because of the respectivecoincidence. It should be appreciated that not all constituentstructures 1005, truncated octahedra 1008, edges 1013 a, vertices 1013b, and truncated octahedral blocks 1034, are designated by referencenumerals in FIG. 23 to preserve clarity.

Referring collectively to FIGS. 22-24, substance collection framework1010 of sampler 1000 is further described; where like reference numeralsrefer to like features previously described. Truncated octahedralframework 1010 is a form of tessellation 1032 similar to honeycomb 1030.Analogous to the arrangement of honeycomb 1030, framework 1010 may beconceptualized as the merger/union or congruent interconnection of pairsof coinciding bar members 1024 and pairs of coinciding joints 1028 thatcome together as adjacent truncated octahedral frameworks 1015 are fittogether. In other words, in effect, a single bar member 1024 and joint1028 is substituted for each of the respective coincident pairs. Thegeneral coincidence of frameworks 1015 from one to the next facilitatessuch conceptualization, which is analogous to the truncated octahedralblocks 1034 of bitruncated cubic honeycomb 1030. Framework 1010corresponds to a form of wireframe 1011 outlining a bitruncated cubichoneycomb shape. Also, the arrangement of bar members 1024 and joints1028 of framework 1010 collectively define a form of cage 1044. Infurther description, framework 1010 is generally a form of openwork1052, defines a reticular/reticulated structure 1054, and is a type oflattice 1056.

As to internal interspatial and external spatial aspects of framework1010, the alignment of open faces 1017 of hexagons 1020 and rectangles1022 form recesses in the form of internal passages 1040 that intersectone another in several different directions to form a passage network1042. Passage network 1042 defines chamber 1046 bounded by the outermostbar members 1024 and outermost joints 1028. Chamber 1046 is comprised ofadjacent truncated octahedral-shaped chambers 1019 each corresponding toa different truncated octahedral framework 1015 (see also FIG. 22).Internal to framework 1010, interspatial intersections between adjacentchambers 1019 result through open faces 1017/facial openings 1018 thatare defined by corresponding bar members 1024 and vertex joints 1028.Furthermore, outermost facial openings 1018 correspond to externalapertures 1048 that open externally—such that chamber 1046opens/intersects external space through apertures 1048. Only a few ofedges 1013 a, vertices 1013 b, truncated octahedral frameworks 1015,open faces 1017, facial openings 1018, chambers 1019, hexagons 1020,rectangles 1022, bar members 1024, joints 1028, passages 1040, andapertures 1048 are designated by reference numerals to preserve clarity.

Referring additionally to FIG. 25, the construction/formation offramework 1010 is next considered. In the illustrated embodiment,framework 1010 is comprised of a like-shaped support structure core 1062coated with a polymer 1070. Accordingly, in some embodiments, it isdesirable to form support structure core 1062 before any polymer 1070 isapplied so the manufacturing techniques are generally described in termsof support structure core 1062 rather than framework 1010 given thepossible absence of polymer 1070 coating. Nonetheless, in some otherembodiments, support structure core 1062 may be partially or completelycoated by polymer 1070 before or during manufacture. Generally, exceptwhere applicable description is provided in terms of support structurecore 1062 rather than framework 1010, based on the general understandingthat the timing of polymer 1070 coating could greatly vary depending onthe selected manufacturing procedure—understanding for some polymer 1070cannot be applied until after core 1062 is at least partially formed asfurther described hereinafter. Further compositional details aredeferred until FIG. 25 is addressed in detail hereinafter.

While the concept of applying multiple frameworks 1015 to visualize theinternal structure of framework 1010 (and correspondingly supportstructure core 1062) may be informative; it should be understood thatframework 1010 may or may not actually be made from multiple frameworks1015 depending on the selected manufacturing procedure; however,framework 1010, framework 1015, and support structure core 1062 allstill appropriately use the same bar members 1024 and joints 1028 inview of the framework 1015 relationship to framework 1010 and supportstructure core 1062. In some embodiments not amenable to application ofmultiple frameworks 1015, support structure core 1062 is formed from asingle, unitary piece of material—with portions of support structurecore 1062 corresponding to bar members 1024 and vertices 1028 beingintegrally shaped. In such embodiments, laser and/or mechanicalmachining, etching, possibly casting or extruding in whole or in part,or the like may be used to make support structure core 1062. In afurther embodiment, a standard “3-D printing” technique is utilized,such as those shaping a series of layers that are stacked and joinedtogether to provide the desired article. In other embodiments, one ormore of these techniques are utilized to make support structure core1062 from relatively few parts (such as two halves, four quarter parts,or the like) that may be connected together using other suitablemechanical, thermal, and/or chemical joining techniques, some of whichare described further below.

In yet other embodiments, support structure core 1062 may be partiallyor completely assembled by mechanical fasteners, by welding, brazing, orsoldering, by chemical agency, such as bonding parts together withadhesive(s), or the like. In certain forms of such embodiments,framework 1010 is comprised of multiple frameworks 1015 joined together.For such forms, as two frameworks 1015 are fit together, each pair ofcoincident bar members 1024 and joints 1028 may be complementarilyshaped and/or sized to approximate merger/union of each pair into asingle bar member 1024 and a single joint 1028. Coincident joints 1028complementally unite/merge in correspondence with the effectivesubstitution of each pair of bar members 1024 by a single bar member1024. In one variation of such forms, single bar members 1024 and vortexjoints 1028 are substituted for each corresponding coincident pair.Further embodiments combine some or all of these techniques to providesupport structure core 1062 and/or may be partially or completely coatedby polymer 1070 before or during manufacture where appropriate.

In FIG. 25, a diagrammatic, planar cross-sectional view of thethree-dimensional sampler 1000 is depicted; where like referencenumerals refer to like features. The cross-section is taken along aplane approximately parallel to the view plane of FIG. 24 andillustrates sectioned portions 1050 with cross-hatching. The sectionedsampler 1000 further illustrates framework 1010 in part, morespecifically designated as cross-sectioned framework portion 1080. Whilebriefly introduced already, compositional configuration 1060 offramework portion 1080 is more specifically described attendant to thedepiction in the vicinity of the sectioned portions 1050. This depictioncontrasts support structure core 1062 composition (cross-hatched) fromadjacent portions to which polymer 1070 have been applied. Generally, itshould be understood that framework 1010 may be rigid, semi-rigid, orsomewhat flexible. In addition, in some embodiments, thermal performancecompatible with thermal desorption of a collected sample and/or thermalcleaning of sampler 1000 would be desirable, while in other embodimentsdifferent thermal performance is desired. Accordingly, the compositionof support structure core 1062 in one form is comprised of one or moreof: glass, polymeric thermoplastic, polymeric thermoset, glass, metal,metalloid, inorganic oxide, ceramic, and glass-ceramic. In one specificembodiment, the composition of support structure core 1062 includesmetal, metalloid, metal oxide, ceramic, or glass-ceramic. Still a morespecific embodiment is comprised of metal, carbon, metal oxide, ceramic,or glass-ceramic. In another preferred embodiment, the composition ofsupport structure core 1062 includes carbon. In a more favored variationof this embodiment, the carbon composition is anisotropic in terms ofstrength and/or thermal performance. In yet a further favoredembodiment, the support structure core 1062 includes one or more carbonallotropes as previously described. In still another preferredembodiment, the composition of support structure core 1062 includesceramic material. Only a few of sectioned portions 1050 are designatedby reference numerals to preserve clarity.

Compositional configuration 1060 further comprises polymer 1070 appliedto the support structure core 1062 to at least partially coat or coverall surfaces thereof. In one preferred embodiment, polymer 1070 providesan approximately complete covering of support structure core 1062.Internally, the polymer at least partially lines internal passages,chambers, and the like. In an even more favored form, internal surfacesof core 1062 are generally completely lined. Polymer composition may bethe same as any of the embodiments previously described in connectionwith sampler 100.

In application, a selected surface is swiped, skimmed, rubbed, orotherwise contacted with 3-D sampler 1000 in a manner like thatdescribed for sampler 100. Likewise, sampler 1000 may be directed to anyof the various sampling targets previously described in connection withsampler 100. Internal passages 1040 of network 1042/chamber 1046 thatare externally open through intersection with apertures 1048 operateduring the sampling activity to intake various substance(s) of interest(if present in trace amount(s)) and temporarily trap the same withinchamber 1046 or on interstitial bar members 1024 internal to sampler1000 either physically, mechanically, and/or chemically. Such mechanismsmay correspond to those described previously in connection with sampler100 where the influential parameters are of like type. Instrumentation30 or other detection equipment like that previously listed is adaptedto receive 3-D sampler 1000 directly for thermal desorption processingand/or receives the sample by rinsing and/or treatment of sampler 1000with one or more agents to release/prepare the sample. Once prepared,the sample is processed in the previously described manner, asapplicable. In one embodiment, sampler 1000 is of particularapplicability to the collection of uranium, plutonium, and heavy metalsthat typically are released from sampler 1000 through liquidtreatment/rinsing/processing/preparation with appropriate agents asdescribed previously and further described in connection withExperimental Examples 11-13. In a further embodiment particularlydirected to radioisotope nuclear material sampling, (like uranium andplutonium), radioactive decay detection equipment appropriate to theexpected decay type(s)/substance isotopes may be used (alpha particle,beta particle, and/or gamma ray detectors).

Many further embodiments of the present application are envisioned.For-example, a method of the present application comprises: providing asampler including an inorganic fiber core and a polymer applied thereonwith background uranium of less than or equal to 10 ng/g; selecting asurface with dust thereon; collecting at least a portion of the dustwith the sampler; chemically processing the sampler to analyze the dustfor uranium content. In one refinement, the inorganic fiber core iscomprised of at least one of glass, metal, metalloid, inorganic oxide,ceramic, and glass-ceramic and the polymer includes PTFE with backgrounduranium of less than or equal to 1 ng/g. In another refinement, the corematerial is comprised of one or more of: HSG, metal, metalloid, metaloxide, ceramic, glass-ceramic and the polymer is comprised of PTFE withbackground uranium of less than or equal to 0.1 ng/g. In a furtherrefinement, the core is comprised of one or more of: HSG, metal, carbon,and metal oxide and the polymer is comprised of PTFE with a backgrounduranium level of less than or equal to 0.01 ng/g. In an alternativerefinement, the inorganic fiber core is made of carbon and/or S-glassand the polymer is made of PTFE with a background uranium level of lessthan or equal to 0.01 ng/g.

In another example, a method, comprising: providing a sampler includingan inorganic fiber core and a polymer applied thereon; selecting asurface with dust potentially containing one or more heavy metals(previously defined); collecting at least a portion of the dust with thesampler; chemically processing the sampler to analyze the dust for heavymetal content. In one refinement, the inorganic fiber core is comprisedof at least one of glass, metal, metalloid, ceramic, glass-ceramic, andinorganic oxide, and the polymer includes at least one of polymericorganofluorine, polyamide, polyimide, PDMS, PBI, PFSA, and PPPO. Inanother refinement, the core material is comprised of one or more of:HSG, metal, metalloid, metal oxide, ceramic, glass-ceramic and thepolymer is comprised of one or more of: perfluorocarbon, perfluoroether,ETFE, FEP, THV, PVdF, and PPPO. In a further refinement, the core iscomprised of one or more of: HSG, metal, carbon, and metal oxide; andthe polymer is comprised of PTFE. In an alternative refinement, theinorganic fiber core is made of carbon and/or S-glass and the polymer ismade of PTFE.

Another example is directed to an analyte sampler to collect and releaseone or more contraband or undesirable substances, the sampler includes:a woven fabric of S-glass fibers, the fabric having a closed weave ofsatin and/or twilled weave type; a polymer applied to the fabric, thepolymer being comprised of polytetrafluoroethylene; and the samplerhaving a thickness less than or equal to 0.3 mm and a flexural modulusequal to or less than 3 GPa.

A further example is directed to a detection system comprising: asampler including a fabric core with a polymer applied thereto, thefabric core being comprised of S-glass; and a thermal desorption IMSdetector structured to receive the sampler. In a further refinement, thesampler has at least one of: a flexural modulus of greater than or equalto 1 GPa, the fabric core with a thickness of about 0.3 mm or less, anda calcined polymer content in a range of about 20% wt through about 40%wt.

A different example is directed to a method of detecting a contraband orundesirable substance, comprising: collecting the contraband orundesirable substance on a sampler, the sampler including a fabric witha first polymer layer applied thereto and a second polymer layer appliedon the first layer, the fabric being comprised of one or more of: HSG,metal, metalloid, inorganic oxide, ceramic, and glass-ceramic, the firstpolymer layer and the second polymer layer each being comprised of oneor more of: polymeric organofluorine, polyamide, polyimide, PBI, PDMS,PFSA, and PPPO; transferring the contraband or undesirable substancefrom the sampler to detection instrumentation; and detecting thecontraband or undesirable substance with the instrumentation. In onerefinement, the inorganic fiber core is comprised of at least one ofHSG, metal, metalloid, metal oxide, ceramic, and glass-ceramic. Inanother refinement, the core material is comprised of one or more of:HSG, metal, carbon, metal oxide, ceramic, glass-ceramic and the polymeris comprised of one or more of: perfluorocarbon, perfluoroether, ETFE,FEP, THV, PVdF, and PPPO. In a further refinement, the core is comprisedof one or more of: HSG, metal, carbon, and metal oxide; and the polymeris comprised of PTFE. In an alternative refinement, the inorganic fibercore is made of carbon and/or S-glass and the polymer is made of PTFE.

A further example is directed to a method of making a sampler,comprising: providing a fabric core; applying at least a partialparticle fill to the fabric core to alter thermal conductivity of thesampler, the particle fill being comprised of one or more types ofinorganic metallic material; applying polymer to the fabric core;heating the fabric core and the polymer after application to the fabriccore to provide the sampler. One refinement includes heating the fabriccore before the applying of the polymer. Another refinement includesfunctionalizing the core/substrate before polymer application. Still afurther refinement includes the polymer comprising a first polymer layerand further applying a second polymer layer on the first polymer layerthat may be the same composition or a different composition. In onerefinement, the particle fill material is comprised of one or morenanoparticles of: metal, metalloid, and metal oxide, and the polymerincludes at least one of: polymeric organofluorine, polyamide,polyimide, PDMS, PBI, PFSA, and PPPO. In another refinement, theparticle fill material are nanoparticles comprised of one or more of:carbon and metal oxide; and the polymer is comprised of one or more of:perfluorocarbon, perfluoroether, ETFE, FEP, THV polymer, PVdF, and PPPO.In an alternative refinement, the particle fill comprises nanoparticlesincluding one or more of: alumina, nanotubes of carbon, and/or graphene;and the polymer is made of PTFE.

Yet another example is directed to a method of making an sampler for oneor more contraband or undesired substances, comprising: providing aninorganic fabric core defining a surface; performing a silanefunctionalization of the surface to provide an affinity to the one ormore analytes and improved polymer application to the core; applying afirst polymer to the fabric core; heating the fabric core and thepolymer after application to the fabric core to provide the sampler. Onerefinement includes heating the fabric core before the applying of thepolymer. Still a further refinement includes applying a second polymerlayer on the first polymer layer. Alternatively or additionally, anotherrefinement includes applying at least a partial particle fill to thefabric core to alter thermal conductivity of the sampler before theperforming of the silane functionalization, the particle fill beingcomprised of one or more of: metal, carbon, and a metal oxide.

In yet a further embodiment, a device, comprises: a sampler to collectand release one or more contraband or undesirable substances, thesampler including: a woven fabric of S-glass fibers, the fabric having a4 HS weave; and a polymer applied to the fabric, the polymer beingcomprised of polytetrafluoroethylene. Various refinements of this deviceare as follows: wherein the sampler fabric has a thickness less than 0.3mm and a flexural modulus of at least 3 GPa; which includes means forthermally cleaning the sample and thermally releasing the one or morecontraband or undesirable substances from the sampler; and/or whichincludes means for analyzing the one or more contraband or undesirablesubstances released to detect the same.

Next, various alternative embodiments of a 3-D sampler of the typedescribed in connection with FIGS. 22-25 are considered. In one suchalternative, coincident cube-shaped constituents are provided bystructural bar linkages extending in three different approximatelyorthogonal directions and intersecting one another to define adjoiningnodes of four linkages, and corresponding to the shape of a cubichoneycomb and further define external passage openings in differentdirections (approximately orthogonal to one another); where the core isat least partially coated by one or more polymer types previouslydescribed. In certain further alternative embodiments, a 3-D samplercollection framework includes a cage-type structural core comprised of:ceramic, metal, metal oxide, glass, glass-ceramic and/or metalloid,which has structural linkage members and nodal joints corresponding tothe edges and vertices of a convex polyhedron that defines severalpassages opening externally, and with one or more polymers of any of thetypes previously described applied thereto, at least partially coatingthe same. In at least some of these alternative embodiments, the convexpolyhedron is one or more of: a geometric convex uniform honeycomb, aconvex space-filling polyhedron, and an archimedean solid.

Still further alternative embodiments of a 3-D sampler collectionframework includes a cage-type structural core comprised of: ceramic,metal, glass, glass-ceramic, metal oxide, and/or metalloid; at least aportion of which corresponds to approximately a parallelepiped,dodecahedral, icosahedral, cuboctahedral, icoidodechedral, spherical,ellipsoidal, cylindrical, conical, or truncated-cone shape made ofadjoined structural linkage members representative of correspondingedges and vertices and that define several passages externally openingin different directions; where the core is at least partially coated byone or more polymer types previously described.

In yet another alternative embodiment, a structural core comprised ofone or more of: metal, ceramic, glass, metal oxide, glass-ceramic,and/or metalloid includes a number of passages that are formed byapproximately helical coils joined together; where each coil externallyopens to collect and trap a substance that is a sampling target and towhich a previously described polymer may be applied to provide at leasta partial coating.

Still certain other alternative 3-D sampler embodiments differ fromthose previously described by lacking any generally discernable solidgeometry classification, and may include a random or pseudorandomarrangement of structural members; where such members defined a 3-Dopenwork, cage, lattice, reticular, and/or other backbone structureproviding: recesses that define external openings thereto and/or mayrecede inward sufficiently to provide a passage into the structure thatmay intersect another passage or chamber, or may extend therethrough;and/or passages defining external openings. Such recesses/passages withexternal openings receive and trap substance(s) targeted for samplingand may be at least partly coated by one or more polymers previouslydescribed.

Further alternative embodiments are directed to a 3-D sampler providedin the form of a pad including a structural core comprised of one ormore of: glass, metal, ceramic, metalloid, and glass-ceramic, thatdefines a number of passageways each externally opening along at leastone face of the pad; where the core is coated by a polymer previouslydescribed. Other alternative embodiments include one or more of thetreatments, options, enhancements, and/or processes previously describedin connection FIGS. 1-21, including, but not limited to: (a) surfaceactivation by silanization or other functionalization procedure; (b)specifically processing to provide a surface phenol functional group;(c) at least partly filling with particles (such as nanoparticles) of ametal oxide (including without limitation alumina), a metal, one or moreallotropes of carbon, and/or a different element or compound; (d)providing two or more applications of polymer—such applications eachbeing the same or different compositions; (e) providing a polymerthickness in accordance with any of the previously disclosed ranges orother limits; (f) applying polymer in any of the alternative % wtlistings previously described; and/or any others as previously describedwith any of FIGS. 1-21 herein.

In another embodiment, a method to detect as substance, includes:collecting the substance with a sampler including a structural core, thestructural core being comprised of one or more of: ceramic, metal, andmetalloid; a polymer applied to at least partially coat the core, thepolymer being comprised of one or more of: polymeric organofluorine,polyamide, polyimide, PBI, PDMS, PFSA, and PPPO; the sampler definingseveral recesses therein that externally open to receive the substance;transferring the substance from the sampler to detectioninstrumentation; and detecting the substance with the instrumentation.In one refinement, at least some of the recesses may be defined byexternal openings with passages receding into the core.

Still another embodiment is directed to a system, comprising: means forcollecting a substance, the collecting means including a structuralcore, the structural core being comprised of one or more of: glass,polymeric thermoplastic, polymeric thermoset, ceramic, metal, metaloxide, metalloid, and glass-ceramic; means for at least partiallycoating the structural core; the structural core including means fordefining several recesses and/or passages extending into the structuralcore that externally open to receive the substance; means fortransferring the substance from the collecting means to detectioninstrumentation, the detection instrumentation including means foranalyzing the substance.

Yet another embodiment is directed to a method to detect a substanceincluding uranium, comprising: collecting the substance with a samplerat least partially coated with a polymer; performing liquid extractionof the substance from the sampler after the collecting of the substancewith the sampler; and detecting the uranium in the substance from theliquid extraction. In one form, the polymer includes PTFE. In anotherform, the polymer comprises any of those previously described inconnection with polymer application to a core.

A further embodiment is directed to an apparatus to detect a substanceincluding uranium, comprising: means for collecting the substance, thecollecting means being at least partially coated with a polymerincluding PTFE; means for performing liquid extraction of the substancefrom the collecting means; and means for detecting the uranium in thesubstance from the liquid extraction. In another form, the polymercomprises any of those previously described in connection with polymerapplication to a core.

EXPERIMENTAL EXAMPLES

The following experimental examples are exemplary only, being empiricalin character, and should not in any way limit the inventions defined bythe claims set forth herein.

Example One

This first experiment was performed with a sampler prepared inaccordance with process 400 at Pacific Northwest National Laboratory(PNNL), a facility managed by the Assignee of the present application.This PNNL sampler was made from S-glass/4 HS woven fabric with PTFEpolymer applied thereto. The fabric thickness was less than or equal toabout 0.3 mm and PTFE application was less than or equal to 35% byweight. The PTFE coating was created by painting a colloidal slurry ofsuspended particles on the core fabric surface followed by evaporationof the solvent. The slurry was prepared using DUPONT TEFLON PTFE TE-3859aqueous dispersion. It contained negatively charged, 0.05 to 0.5micrometer (μm) PTFE resin particles suspended in water, and about 6%(by weight of PTFE) of a nonionic wetting agent and stabilizer.

The PNNL sampler was compared to sampling swipes sourced from: (a)SARFRAN MORPHO (MORPHO) and (b) DSA DETECTION (DSA). The DSA and MORPHOsampling swipes used for the comparison were commercially availablematerials. Data was taken with a BARRINGER IONSCAN 400A ion mobilityspectrometer (SMITHS DETECTION) via thermal desorption. This instrumentwas operated in negative ion mode at a thermal desorption temperature of180° C. and a collection time of 10 s. The drift and inlet temperatureswere set at 114° C. and 240° C., respectively. The sample gas was set at239 mL/min and the drift gas at 351 mL/min, as per standard instrumentsettings.

FIG. 9 is a comparative graph illustrating magnitude versus timeresponses of samplers from the three different sources to a 10 nanogram(ng) sample of TNT (hand spiked) as detected with the indicated IMSdetector. Describing the data plots in top to bottom order of the insetlegend: (1) the “X” data point plot represents the response of the PNNLsampler embodiment of the present application—it has the highest peakand quickest peak response, (2) the “hollow triangle” (Δ) data pointplot represents the response of the MORPHO brand of sampler that isintermediate in terms of peak magnitude and speed, and (3) the “filleddiamond” (♦) data point plot represents the response of the DSA brand ofsampler with the slowest and lowest peak response. The relatively higherresponse of the PNNL sampler illustrates its superior performance underlike conditions. It is theorized that the use of a relatively thinS-glass for the fabric core and/or a relatively modest amount of PTFEpolymer resulted in higher thermal conductivity, higher gaspermeability, and reduced thermal mass to provide a better TNT signalresponse of the PNNL sampler.

Example Two

This second experiment compared the responses of differently preparedPNNL samplers to a TNT 10 ng sample, as reflected in Table I thatfollows:

TABLE I Average of IMS signal of Sampler Material 10 ng TNT Core thickE-glass 351 Core thick S-glass 555 Core thin E-glass 588 Core thinS-glass-phenyl 911 Core thin S-glass-phenyl-PTFE 781

For Table I, data was taken with a BARRINGER IONSCAN 400A ion mobilityspectrometer (SMITHS DETECTION) using conditions/parameters like thosefor Example One. The different sampler configurations correspond to theentries in the left hand column of Table I. The maximum TNT signal fromthe sampling material was averaged and reported in the right hand columnof Table I. The first three entries of Table II resulted from samplestaken with three different core/substrate material configurationswithout application of a polymer thereto, which in like order (top tobottom) are: thick E-glass core, thick S-glass core, and thin E-glasscore. The fourth entry of Table I is for a sampler prepared from thinS-glass and functionalized per operation 414 of process 400 to providephenyl terminal groupings (See FIG. 7), but still lacking any polymerapplication. The fifth and final entry of Table I is prepared in thesame manner as the fourth sample, but also has PTFE polymer applied inaccordance with operation 416 of process 400. It has been discoveredthrough such experimentation that the application of a polymer like PTFEmay controllably increase stiffness of the sampler as a function of theamount applied and other operations/treatments, such as heat applied tocure the PTFE.

Table I relates to properties and parameters useful for the developmentof suitable samplers with varying stiffness, including: the compositionof the substrate/core (in this case E-glass or S-glass), substrate/corethickness (whether “thick” or “thin”), surface chemistry(functionalization), and polymer application. For a given core type andthickness, the sampler stiffness can be controlled with the amount ofpolymer applied and/or heat treatment used to cure the polymer. Acertain degree of stiffness/flexure is desired in some embodiments toprovide for more suitable handling, detector equipment interfacing, andlongevity, among other things. It should be appreciated that the fabriccore sampler material of S-glass fibers provides higher IMS signals ascompared to E-glass fibers even without functionalization (like that ofoperation 414) or polymer application (like that of operation 416),which is theorized to be due to its better thermal properties. Indeed,the thinner sampler core appears to significantly improve the IMSsignal, which may be because of improvement in mass transport of theanalyte out of the sampling material during a thermal desorption analyterelease/transfer. The phenyl silane surface functionalization of thinS-glass (fourth entry of Table I) indicates performance improvementrelative to TNT release. Per the fifth/final entry of Table I, the PTFEpolymer application to the core and functionalized thin S-glass corecombination provides the stiffness and other properties desired for somerobust applications; however, indicates a trade-off in terms of aslightly reduced IMS signals. This reduction is most likely due to thechange of mass transfer and/or surface chemistry alteration because ofthe PTFE application.

Example Three

Experimental Example Three relates to the varying performance ofdifferent PTFE-coated core/substrates used for trace analyte detection(See FIG. 10). It should be appreciated that a thermal desorptionsampler used with IMS, gas chromatography, or the like preferably hasgood thermal conductivity and low specific heat capacity to facilitaterapid desorption heating. A comparison of these properties for variouscandidate core/substrate materials at 25° C. was determined as providedin Table II as follows:

TABLE II Thermal Specific Conductivity heat capacity Core Material(W/m-K) (J/g-° C.) E-glass Fiber^(A,B) 1.28-1.32 0.78-0.82, 0.803S-glass Fiber^(A,B) 1.44-1.46 0.72-0.75, 0.736 Stainless Steel^(C,D)16.2, 10-30 0.5, 0.2-0.62 Carbon Fiber^(E,F) 21-180, 10 0.795 Al₂O₃^(G-J) 28-35 0.45-0.955, 0.78 Polyamide^(K) 0.23-0.29 1.26-1.7  PTFE^(K)0.25 1.0 PVDF^(L) 0.19 1.2-1.6 PDMS^(M) 0.25 1.46 Cotton/muslin^(N)0.071 1.335 Cellulose^(N) 0.242 1.338 Polytetrafluoroethylene^(C) 0.251.00 Silica^(O) 1.30 0.937 Nichrome V^(C) 14.0 0.480 Titanium^(C) 17.00.528 Nickel^(C) 60.7 0.460 Platinum^(C) 69.1 0.134 Iron^(C) 76.2 0.440Tungsten^(C) 163 0.134 Aluminum^(C) 210 0.900 Gold^(C) 301 0.128 (25°C.) Copper^(C) 385 0.385 Silver^(C) 419 0.234 A. JPS Composite Materialsdatabook. http://jpsglass.com/ B. Lubin, G. Handbook of fiberglass andadvanced plastics composites, Robert E. Krieger Pub. Co.: Huntington,N.Y, 1969. C. MatWeb Material Property Data.http://www.matweb.com/index.aspx D.http://www.lenntech.com/stainless-steel-3161.htm E.http://www.christinedemerchant.com/carbon_characteristics_heat_conductivity.htmlF. http://www.aerosol.co.il/files/article/1315850055u55QN.pdf G. Lu, X.and Xu, G. Thermally conductive polymer composites for electronicpackaging, Journal of Applied Polymer science, 1998, 65, 2733-2738. H.http://www.engineeringtoolbox.com/thermal-conductivity-d_429.html I.http://aries.ucsd.edu/LIB/PROPS/PANOS/al2o3.html J.http://www.azom.com/properties.aspx?ArticleID=52 K. Martienssen, W. andWarliment, H (Eds). Springer Handbook of Condensed Matter and Materialdata, Spinger Berlin Heidelberg.: Germany, 2005. L.http://fluorotherm.com/Properties-PVDF.asp M.http://www.mit.edu/~6.777/matprops/pdms.htm N. Curtis, L. J., Miller, D.J., Transport Model with Radiative Heat Transfer for Rapid CellulosePyrolysis. Ind. Eng. Chem. Res., 1988, 27, 1783-1788 O.http://www.tekna.com/powder/spherical-powder/silica.htmlFrom Table II, it was observed that metal (like stainless steel, rowthree of Table II), carbon (row four of Table II), and metal oxide (likealumina, row five of Table II) have thermal conductivity (column two ofTable II) and specific heat (column three of Table II) parameters betterthan glass fibers (such as E-glass and S-glass, respectively rows oneand two of Table II), making them attractive as sampler materials from athermal desorption perspective; however, other considerations can limitapplication. For instance, carbon, stainless steel, and other metalmeshes/fabrics tend to be expensive compared to glass fiber fabrics, andsurface functionalization of proved more difficult. Metal oxides havesimilar limitations. Furthermore, these materials can scratch certaintest article surfaces. Also, carbon surfaces can promote rapid oxidationof TNT through TNT methyl groups, and may chemically interact with otheranalytes in an unacceptable manner. Nonetheless, it has been found thata carbon core fully covered with PTFE exhibits excellent release of TNTfor thermal desorption purposes. Nonetheless, all these metals, metaloxides, carbon, and the like can find application in certainembodiments—especially depending on target analyte(s) and particulartreatments applied thereto. In FIG. 10, results for other PTFE-coatedcore materials are graphically presented as comparative plots ofmagnitude versus time responses of samplers to a TNT 10 ng sample usingthermal desorption IMS with setup/conditions comparable to ExperimentalExample One. For Example Three, 6-10% wt PTFE coating was applied toeach core and all samples were heated at 400° C. in a furnace for 30minutes prior to testing.

Describing the data plots in top to bottom order of the inset legend:(1) the “filled diamond” (♦) data point plot represents a PTFE-coatedstainless steel core response—it has the highest peak; (2) the “filledcircle” (●) data point plot represents a PTFE-coated thin S-glass coreresponse—it has the second highest peak; (3) the “filled square” (▪)data point plot represents a PTFE-coated thick S-glass core response—ithas the third highest peak; and (4) the “filled triangle” (▴) data pointplot represents a PTFE-coated thick E-glass core response—it has thelowest peak. Per FIG. 10, PTFE-coated stainless steel had better TNTrelease performance than PTFE-coated glass fibers of the E- orS-type—theorized to be due to stainless steel's higher thermalconductivity and lower specific heat compared to glass fibers per TableII.

Both Examples Two and Three demonstrated that a thin core materialreleases the analyte faster—providing a higher and sharper peak comparedto a thick core/substrate material with the same surface chemistry. Fromthis empirical information, it is theorized that a thinner samplerreduces the thermal mass, and further improves thermal desorptionrelease while decreasing desorption time at which the maximum signal canbe achieved. As indicated in Table II, S-glass fiber has intrinsicallybetter thermal properties (higher thermal conductivity and lowerspecific heat) than E-glass fiber, which results in faster thermaldesorption of the analytes. As can be observed by the area under theresponse plots, S-glass fiber releases a larger fraction of the spikedanalyte compared to E-glass fiber in Example Three.

Example Four

Referring to FIG. 11, the influence of fabric weave and yarn pattern forglass fiber was demonstrated. FIG. 11 presents a graph that comparedmagnitude versus time responses of two samplers with different cores toa TNT 10 ng sample when tested by IMS under experimentalsetup/conditions comparable to those described for Experimental ExampleOne. Describing the data plots in top to bottom order of the insetlegend: (1) the “X” data point plot represents the response of a 4 HSweave pattern comprised of thin E-glass fibers with 225 yarn pattern—ithas the highest peak, and (2) the “hollow triangle” (Δ) data point plotrepresents the response of an 8 HS weave pattern comprised of thinS-glass fibers with 450 yarn pattern—it peaks at a slightly lower value.Both plots peak at comparable times. There are inset computer-generatedimages of the 4 HS and 8 HS weaves with like labeling. Both the E-glassfiber 4 HS weave/225 yarn pattern fabric sampler and S-glass fiber 8 HSweave/450 yarn pattern fabric sampler had approximately the same fabricthickness of 0.1 mm with similar (˜25%) PTFE weight coating, and bothwere treated at 340-375° C. in a furnace for 2 minutes.

FIG. 11 indicated how the core weave pattern can impact particle pickupand analyte recovery. As shown therein, the 4 HS weave with 225 yarnstrand weight/count (typically in strand yards per 0.01 pound=yards/0.01lb.) on thin E-glass fiber fabric is significantly more efficient atreleasing TNT from the sampling surface than the 8 HS weave with 450yarn strand weight/count on thin S-glass fiber fabric despite betterthermal conductivity and lower specific heat of the S-glass fiberfabric. Because the E-glass fiber results are better, it indicates theimpact weave pattern can have on analyte recovery. It is theorized thatthe enhanced desorption of the E-glass fabric results from the highergas permeability of the 4 HS weave/225 yarn strand weight/count comparedto the 8 HS weave/450 yarn strand weight/count of the S-glass fabric.From this experiment, it is theorized that higher gas permeabilityresults in better analyte mass transport of the thin material. Data wastaken on the same day and with the same instrument. Suitable weave/yarnpattern varies with the application and detection system used.Typically, different detection systems also may have different responsesto released analytes. The weave and yarn pattern also significantlyimpacted the collection of materials from the surface. It ishypothesized that S-glass material should be a higher grade weavematerial for superior performance. Moreover, for installation of surfacechemistry silanes per the '910 patent, S-glass may be a better substrateas it generally contains a higher density of surface silanol sites forligand loading than E-glass.

Overall, Tables I & II, and FIGS. 10 & 11 show that thickness, type, andweave/yarn of glass fiber make significant contributions to the thermaldesorption releasing ability of TNT from corresponding samplers. Glassfiber and many other inorganic materials have thermal propertiesacceptable for use as a sampling medium for thermal desorption analysis.Generally, for glass fibers a combination of inorganic oxide compoundsform active surfaces for collection of analyte(s). Sometimes, theseactive surfaces bind more strongly than desired to target analytes,hampering release. Thus, coating and/or lamination of glass fibers witha suitable material, such as PTFE, can provide an attractivealternative. Polymer composition and other characteristics can be variedto serve different purposes, such as to: cover overly active glass fibersurface sites, provide a desired degree of sampler stiffness/rigidity,increase target analyte collection ability, and enhance thermaldesorption of target analyte(s).

Example Five

Various polymer coatings on thin S-glass were studied and compared forTNT release capability as set forth in Table III as follows:

TABLE III Average IMS Thermal signal of 10 ng Polymer Coatingdecomposition (° C.) TNT PTFE 448 503 PDMS 250 121 PVdF 355 5 PBI 540 0TENAX TA 502 352 TENAX TA after PTFE coating 448 438 TENAX GR 502 302TENAX GR after PTFE coating 448 496

In Table III, all polymers were coated on thin S-glass with a 3% wt-6%wt concentration range, except for PTFE and PDMS, where 20% wt was used.After coating, the samplers were then thermally treated at temperaturesof 120-150° C., except for the PTFE coating, which was treated at 360°C. Thermal decomposition information of Table III was obtained viaThermal Gravimetric Analysis (TGA) data. The maximum TNT signal from thesampling material was averaged and reported. IMS setup/conditionscomparable to those for Experimental Example One were utilized.

The thin S-glass fiber fabric qualitatively acquired increasedstiffness/rigidity after being coated with these polymers, as did otherpolymers, except in the case of PDMS. The PTFE polymer provided thehighest signal for TNT thermal desorption release when compared to theother polymers (Table III). Surprisingly, there was no occurrence of TNTsignal from PBI, which is known to have high thermalstability—suggesting that some polymer compositions demonstrate betteradsorption ability than desorption for TNT. TENAX TA (PPPO) and TENAX GR(PPPO/graphite) demonstrate TNT desorption behavior of more interestthan several of the other polymers. The release of TNT was pronouncedwhen TENAX was coated after PTFE coating to provide a double coatinglayer of different polymer compositions (PPPO or PPPO/graphite on PTFE)of the type illustrated in FIG. 7. While these mixed polymers tend to bemore responsive than some other polymer applications, these mixedpolymers did not provide a better TNT release signal than the PTFEcoating alone in this experiment. Both TENAX TA and TENAX GR polymerswere obtained from dissolved beads of the same. The beads were dissolvedin dichloromethane for a few days or until the beads were mostlydissolved.

Example Six

For Experimental Example Six, PTFE-coated thin fiber S-glass was chosenfor further study and development because it provided the highest signalof TNT thermal desorption release in conjunction with high thermalstability (high thermal decomposition temperature in Table III). PTFE isrelatively chemically inert, thermally stable, and highly hydrophobic,and the surface properties and structures of PTFE change as a functionof cure temperature. At room temperature, PTFE stock is typically awhite, fine powder; but its physical morphology/structure becomes theextended chain type by curing it at a temperature above its meltingpoint and also becomes more transparent/translucent. Simultaneously,cure temperature can influence sampler stiffness/rigidity (or converselyflexure) as quantified by flexural modulus determinations, and samplersurface property changes. The proper heat treatment of PTFE applied toglass fiber fabric can significantly contribute to the stability,stiffness, and surface properties of the corresponding sampler with aglass fiber core having PTFE applied thereto.

FIG. 12 indicates a PTFE coating treatment temperature in the range fromthe PTFE melting point to the PTFE thermal decomposition temperaturethat can provide desired sampler stability, stiffness, and surfaceproperties. FIG. 12 presents a comparative graph illustrating magnitudeversus time response for each of four different samplers to a TNT 10 ngsample when tested with IMS with setup conditions comparable to thosefor Example One. Each of these different samplers were subjected to adifferent heat treatment as reflected by the FIG. 12 inset legend. In atop to bottom order of this inset legend: (1) the “hollow triangle” (Δ)data point plot represents the response to approximately a 450° C. heattreatment, which has the second highest peak; (2) the “X” data pointplot represents the response to approximately a 400° C. heat treatment,which is the highest peak; (3) the “filled triangle” (▴) data point plotrepresents the response to approximately a 325° C. heat treatment, whichis the third highest peak; and (4) the symbol “*” (an “X” with avertical line intersecting its cross-point) provides a data point plotrepresentative of the response to approximately a 150° C. heattreatment, which has the lowest peak. Peak timing is comparable for allthe plots. Each sampler was comprised of a 10% wt PTFE coating on thinfiber S-glass fabric, and did not have phenyl surface or otherfunctionalization. All samplers were placed in a furnace at theindicated temperature for 30 minutes.

As reflected in FIG. 12, PTFE coatings on thin S-glass fiber fabricswere heat-treated at different temperatures including, below its meltingpoint (150° C. and 325° C.), above its melting point (400° C.), and nearits thermal decomposition temperature point (450° C.). Higher stiffnessor rigidity was obtained with increased heat treatment temperature,which can be mechanically/quantitatively represented by increasingflexural modulus of the sampler. The PTFE-coated sampler heat-treated at400° C. demonstrated a higher and sharper peak of TNT thermal desorptionrelease than the other samplers heat-treated at 450° C., 325° C., and150° C.

Based on Experimental Example Six, the PTFE-coated sampler surfaceproperties and structure seem to change with different heat treatmentsand correspondingly impact TNT thermal desorption release performance.Scanning Electron Microscope (SEM) and contact angle measurements ofPTFE-coated samples were conducted for a better understanding. Contactangles can be used to measure the wettability of surfaces. Themeasurement indicated the degree of wetting when liquid is deposited ona surface. A low value, <90 degrees, indicates a wettable surface, andis observed when liquid spreads well on the surface. This value rangealso demonstrates the hydrophilicity of the surface. A contact angle of0 degree means that complete wetting has occurred. A higher value, >90degrees, indicates poor wetting, and is observed when liquid beads onthe surface. Accordingly, hydrophobic surfaces measure between 90 and180 degree contact angles. FIGS. 13-20 provide a sequence ofcomputer-generated SEM images of PTFE-coated surfaces on both fabric anda silicon (Si) wafer heated at 150° C., 325° C., 400° C., and 450° C.,respectively. The PTFE coating was created by painting a colloidalslurry of suspended PTFE particles on the sampler surface followed byevaporation of the solvent. The slurry was prepared using DUPONT TEFLONPTFE TE-3859 aqueous dispersion. This dispersion contains negativelycharged, 0.05 to 0.5 μm PTFE resin particles suspended in water, whichalso contains approximately 6% (by weight of PTFE) of a nonionic wettingagent and stabilizer.

FIGS. 13 and 14 are computer-generated SEM images of the thin S-glasssampler fabric and Si wafer, respectively, with the coating dried at150° C. which removes the solvent/water of the applied aqueousdispersion. FIG. 13 corresponds to a contact angle in the range of 0-10degrees and FIG. 14 corresponds to a contact angle in the range of 50-90degrees. FIGS. 15 and 16 are computer-generated SEM images of thesampler fabric and Si wafer, respectively, with the coating calcined at325° C. and baked to remove the nonionic wetting agent (typically at290° C.). FIG. 15 corresponds to a contact angle in the range of 45-65degrees and FIG. 16 corresponds to a contact angle in the range of 70-95degrees. From the SEM images, a granular form of PTFE is observed withsintering and voids in PTFE structure for the 325° C. heat treatment.Based on the contact angle values, samplers prepared at this temperatureare in the range indicating hydrophilic surfaces.

FIGS. 17 and 18 are computer-generated SEM images of the sampler fabricand Si wafer, respectively, with the coating calcined at 400° C. whichis above the crystalline melting point of the PTFE resin particles (thePTFE melting point is approximately 327° C.). FIG. 17 corresponds to acontact angle in a range of 95-105 degrees and FIG. 18 corresponds to acontact angle in a range of 90-100 degrees. The PTFE particles/granularforms change from white to mostly transparent material with thistreatment temperature. The computer-generated SEM images reveal acompletely different, transformed morphology, in which the extendedchain structure/folded chain structure can be seen. Besides thecrystalline morphology change, bridges formed between the fibers ofglass can be observed for the 400° C. treated PTFE-coated sampler. Basedon empirical data, t is believed that this heat treatment may improvethe thermal conductivity of the glass fiber fabric core and PTFEcombination due to changes in crystallinity of the PTFE and reduction invoids through better contact of the PTFE with the glass fibers of thesampler fabric. The contact angle demonstrates that the surface of asampler prepared at this temperature is hydrophobic, which is generallyfound for detection sampler operation, as previously described.

FIGS. 19 and 20 are computer-generated SEM images of PTFE coatingcalcined at 450° C., which is approximately the decompositiontemperature of PTFE (See Table III). For FIG. 19, a contact angle in arange of 80-95 degrees was determined and for FIG. 20 a contact angle ina range of 90-105 degrees was determined. The material demonstrated asimilar morphology and contact angle as the PTFE-coated Si waferobtained at 400° C., but with longer polymer chains. However, on thePTFE coated fiber S-glass fabric, a poorer coating and lower contactangle is observed, which may be due to the PTFE starting to decomposebased on empirical observations. Shrinking of PTFE film can be observed,which results in a greater tendency for direct interaction between theglass fiber surface and analyte(s) as compared to the 400° C. heattreatment.

Accordingly, heat treatment at 150° C. and 325° C., which are both belowthe PTFE melting point, appear to still allow the spiked TNT analyte todirectly contact and interact with the active surface of the glass fiberfabric because the PTFE morphology was relatively unaltered. As aconsequence, a lower TNT desorption signal results. A similar outcome isobserved for the PTFE-coated sampler subjected to the 450° C. heattreatment. While 450° C. was above the PTFE melting point, it isapproximately the same as the empirically-determined PTFE thermaldecomposition temperature (448° C. per Table III). The highest signal ofTNT thermal desorption is obtained from the PTFE-coated sampler with the400° C. heat treatment. This heat treatment resulted in a hydrophobicsurface with a more uniform coating appearance, which is believed toreduce direct contact/interaction between the TNT analyte and the glassfiber surface.

Example Seven

Applying a thin, incomplete polymer coating with intermittent coverageof the glass fibers enables gas or liquid phase analyte(s) topreferentially bind to the fiber surface regions where the polymercoating is missing or exceedingly thin to a greater degree than wherethe polymer coating is thicker/more complete. Furthermore, when a thincoating is applied to a glass fabric, the corresponding weave structuresreduce the degree of coverage such that the thin coating may be unableto completely cover the active core sites of the fabric, resulting inrelatively stronger binding between analyte(s) and the fabric surface.Consequently, less efficient detection of the target analyte(s) result(i.e., no thermal desorption release or decomposition of TNT). Betterdetection can result if a thicker, more complete polymer coating isapplied and/or by silane functionalization of the fabric surface priorto the polymer coating. In contrast, a coating that is too thickundesirably slows analyte release (reduces instrument signal) due to thereduction of thermal conductivity of the sampler. As a result,concentration or thickness of the polymer coating involves trade-offsfor each application or detection system type. Moreover, it has beenunexpectedly discovered that in certain cases it is more favorable tomake multiple thin coatings on the fiber core/substrate for improveduniformity as opposed to a single thick coating deposition (See FIG. 7).In some embodiments, multiple coatings of the same type of polymer areapplied to the fiber substrate/core, which may be a fiber fabric or anonfabric fiber conglomeration; while in other applications, multiplecoatings of different compositions/types of polymer are applied to thefiber substrate/core, which also may be a fiber fabric or a nonfabricfiber type.

Experimental Example Seven explored the performance of fibersubstrates/cores with different PTFE deposition concentrations for eachof three different heat treatment (cure) temperatures. As shown in TableIV below, PTFE in solution concentration by % wt (% wt loadings) wereachieved in a couple of different ways: (1) multiple coating layers(dippings) (see second column of Table IV), and (2) use of differentsolution concentrations (see third column of Table IV):

TABLE IV PTFE in solution PTFE IMS signal of 10 ng TNT Con-Concentration Heat Heat Heat centration Coating in coating treatmenttreatment treatment (% wt.) layer (% wt.) at 325° C. at 400° C. at 425°C. 0 0 0 150 150 120 7.5 1 4 196 198 216 15 1 12 183 334 372 22.5 1 16316 439 406 30 1 20 329 497 534 22.5 2 24 348 580 558 30 2 30-35 436 597635 30 3 41-45 306 563 546

All entries in Table IV employed a thin S-glass fabric core each treatedat the indicated temperatures of about 325° C., 400° C., or 425° C. forabout 30 minutes. The maximum TNT signal from the sampling material wasaveraged and reported; using IMS experimental setup/conditionscomparable to those for Experimental Example One. It should beappreciated that uncovered core structures can result in irreversiblebinding of some analytes, as well as the potential for reactivedegradation/loss of analytes, which can apply to certain organic speciesas well as metal species, such as uranyl nitrate and uranyl fluorides.

From Table IV, it was empirically demonstrated that the concentration ofpolymer coating materials impacted analyte capture and mass transfer inthe materials. While thicker coatings typically resulted in bettersurface passivation, reduced thermal mass flow and reduced thermalconductivity were companion traits. For rapid thermal desorptionrelease, faster thermal mass flow, and to satisfy requirements of traceanalyte detection instrumentation; there frequently are trade-offsfavoring a somewhat thinner coating to provide better utility forsurface sampling applications. In the case of PTFE, the concentration ofPTFE not only affects the film thickness, but also tends to impact thephysical properties/morphology of the sampler surface.

In Example Seven, as reflected in the Table IV entries, glass fibersamplers were coated with selected coating masses (given as % wt ofentire swipe) and then heated to different temperatures of about 325°C., 400° C., and 425° C., respectively, for approximately 30 minuteseach. Higher rigidity/stiffness/flexural modulus and hydrophobicityresulted from increased PTFE concentration. The samplers prepared atdifferent temperatures demonstrate a similar response tendency alongwith increasing PTFE concentration (Table IV). The IMS signals of TNTrelease were more pronounced with increased concentrations of PTFE up toabout 35% wt for the indicated experimental setup. The higher surfacehydrophobicity generally resisted polar solvents and analytes enteringand diffusing into/through PTFE, which resulted in less chance of TNTcontacting undesired active sites on the core surface underneath thePTFE. After solvent evaporation, TNT typically stays on the hydrophobicsurface of PTFE, therefore, a higher TNT thermal desorption releasesignal is obtained.

Samplers prepared at approximately 325° C. demonstrated a lower signaland less rigidity/stiffness—having little or no PTFE melting. On theother hand, higher signals and higher rigidity/stiffness, were obtainedfrom both higher temperature samples at approximately 400° C. and 425°C. These high temperatures exceed the melting temperature of PTFE ofabout 330° C. but remained below the thermal decomposition temperatureof about 448° C., which facilitates transformation of the PTFE particlesto extended chain morphology (See also, FIGS. 13-20 and accompanyingtext). These results tend to indicate that sampler rigidity/stiffnessincreases with polymer melting—such melting appearing to bind corefabric fibers together. Even with relatively thicker PTFE samplercoatings, a thin S-glass fabric sampler core still provided better TNTrelease when compared with commercial swipes.

Example Eight

Many core materials with desirable physical/thermal properties haveactive surfaces which bind analyte(s) without dependable release,reducing the corresponding detection signal. Frequently such materialshave polar surfaces, which tend to disrupt uniform polymer coverage.Installation/functionalization of surface chemistries on core materialscan act as an interfacial layer that provides better polymer coating andbetter performance of the samplers. In addition, functionalization ofthe substrate/core surface promotes uniform spread of the polymer andpassivates the fiber surface that may be exposed through imperfectpolymer coverage or accidental removal of the polymer layer (i.e.scraped off). High density organo-silane layers can serve as orfacilitate formation of a functionalized surface layer as detailed inthe '910 patent. An interfacial layer provided by phenyl silanes likedepicted in the partial perspective view of FIG. 7, are among those thatare thermally stable and compatible with TNT collection/release.

The comparative plots of the graph presented in FIG. 21 illustrate theeffect of surface chemistry on thin fiber S-glass for 10 ng TNTdetection using IMS with experimental conditions and setup comparable tothat for Experiment One. More specifically, the comparative graph ofFIG. 21 depicts the 10 ng TNT response of each of three different formsof PTFE-coated samplers with an S-type fiberglass core, two with and onewithout phenyl surface treatment of the core. The graph presentsmagnitude versus time of the three sampler responses. Following the topto bottom order of the inset legend: (1) the “X” data point plotrepresents the response of a phenyl-PTFE sampler configuration heattreated at approximately 150° C.—it has the highest peak, (2) the“hollow triangle” (Δ) data point plot represents the response of aphenyl-PTFE sampler configuration heat treated at approximately 400°C.—it has an intermediate peak, and (3) the “hollow diamond” (⋄) datapoint plot represents the response of a PTFE sampler configurationwithout functionalization, and heat treatment at approximately 400°C.—it has the lowest peak. All three plots peak at comparable times. Forall three samplers, a coating of 10-15% wt PTFE was utilized with heattreatment, each for thirty (30) minutes, at the two temperatures, 150°C. and 400° C.

Example Nine

As per the previous descriptions, surface functionalization applied tothe core material of an appropriate type has been surprisingly found toprevent strong binding interactions of the core with the analytes (i.e.,TNT) that may potentially interfere desired performance (such aseffective thermal desorption). Surface functionalization has been foundto impact performance of samplers as demonstrated by priorexperimentation (See FIG. 21). A phenyl silane core surfacefunctionalization prior to coating a polymer such as PTFE candemonstrate a significantly higher release signal than anunfunctionalized surfaces to which PTFE is applied. This difference mayresult because the phenyl groups can prevent the binding of TNT toundesired trapping/active sites of the core. The effect of surfacefunctionalization on a thin fiber S-glass fabric sampler is furtherdemonstrated by Experiment Nine data organized in Table V as follows:

TABLE V Curing Surface temperature IMS signal Functionalization (° C.)of 10 ng TNT None 325 269 None 400 497 Phenyl 325 596 Phenyl 400 598For Table V, the samplers with and without phenyl functionalization werecoated with ˜30 wt % PTFE solution and then cured at 325° C. or 400° C.to result in ˜20 wt % of PTFE after curing. Phenyl installation wasachieved by phenyl silane functionalization; refluxing the sampler with10% by volume phenyl silane in toluene for 18 hours, and preconditioningin a vacuum oven at 180° C. overnight. The maximum TNT signal fromsampling material was averaged and reported; using IMS experimentalsetup/conditions comparable to Example One.

In Table V, both cure temperatures appear to provide high releasesignals for TNT. Although, for the thin coating of 10-15% wt PTFEreflected in FIG. 21, a slightly slower release can be seen from themore rigid phenyl functionalized sampling material treated at 400° C.The morphology of PTFE changes from granular form to extended chainmorphology at this temperature (FIGS. 13-20), which affects the polymerproperties, most likely impacts mass transfer and interactions on thesurface. For thicker coating (>20% wt PTFE, Table IV), slightly lowerrelease signals for TNT were obtained as compared to the thinnercoating. This result is believed to be because of reduced mass transferand thermal conductivity. FIG. 7 provides a conceptual perspective imageof a polymer coated on phenyl functionalized glass core. The phenylsilane (shown as a tethered 6 sided rings P in FIG. 7) provides asurface passivation layer to prevent analyte loss. The interfacialphenyl silane layer provides compatibility with the polymer layer andimproves both adhesion and uniform distribution of the polymer coating.

Example Ten

Many polymers are solvent-resistant and thermally stable; however, theyoften have thermal heat properties (i.e. low thermal conductivity andhigh specific heat as shown in Table II), which is believed to slowrelease of analytes from the surface when using thermal desorptiontechniques common to IMS and other detection instrumentation. It hasbeen surprisingly discovered that for the samplers with PTFE coating,thermal conductivity could be enhanced by adding selected thermallyconductive materials, such as Al₂O₃ (alumina) nanoparticles into thesubstrate/core. The Al₂O₃ nanoparticle has a thermal conductivity around30 W/m-K, ˜100× better than PTFE and 6× better than fiber S-glass. Otherpossible micro of nanoparticles to add include metals, other metaloxides, certain carbon allotropes, ceramics, and glass-ceramics. Morespecifically, Cu, Al, Fe, and Ag are exemplary metals. Other metaloxides include CeO₂, and TiO₂.

Accordingly, Al₂O₃ nanoparticles were added to a thin S-glass fabriccore to test whether faster heating and better analyte release werepromoted. The results of this experimentation were captured in Table VIas follows:

TABLE VI Al₂O₃ Surface Thermal Addition functionalization PTFE TreatmentIMS signal to core of Al₂O₃ Concentration Conditions From (% wt)particles (% wt) (° C.) 10 ng TNT 0.01 None 0 360 197 0.05 None 0 360127 10.0 None 0 360 0 0.01 Phenyl 0 180 548 0.05 Phenyl 0 180 415 10.0None 20 325 227 10.0 None 20 400 576 10.0 Phenyl 20 400 687Al₂O₃ nanoparticles, particle size of about 50 nanometers (nm), werecoated on thin S-glass fiber, and then heat treated at 360° C. for 2hours. Then, the Al₂O₃/S-glass core were functionalized with phenylsilane, and/or coated with 20% wt PTFE, and calcined at 325° C. or 400°C., respectively, as reflected in Table VI.

Because the Al₂O₃ nanoparticles have a high surface area and chemicalactivity, strong retention of analytes can occur, reducing the signalfrom the detection instrumentation. As can be seen in Table VI, thehigher the concentration of Al₂O₃ used, the lower the release signal ofTNT obtained. Therefore, before Al₂O₃ nanoparticles are used for theirenhanced thermal properties; they should be chemically passivated toavoid analyte binding, which can be accomplished by silanization or thinpolymer coating. It is also posited that incorporation of the particlesshould not block mass transfer and air permeability through the samplerduring desorption and detection. Therefore, Al₂O₃-thin S-glass was thenfunctionalized with phenyl silane or coated with 20% wt PTFE. As can beseen in Table VI, the post-functionalizations significantly improve theperformance of the samplers. It provides a much higher release signalfor TNT than those that are not functionalized. The Al₂O₃-thin S-glasscoating with 20% wt PTFE and treated at 400° C. also show the enhanceddesorption of TNT. Accordingly, both post-phenyl functionalization andcoating with 20% wt PTFE of Al₂O₃-filled thin S-glass provides thehighest signal of TNT release. Furthermore, Table VI also shows theconsistent effect/improvement with high cure temperature demonstrated inconnection with the experimentation of FIG. 21, which is believed toinfluence the release of TNT from the unfunctionalized Al₂O₃-fillsamplers. Correspondingly, the curing temperature of 400° C. provides aconsistently high release signal for TNT because of the extended chainmorphology previously described. As a consequence, one favoredembodiment of a sampler material includes a phenyl coated S-glass fiberfabric core with phenyl-coated alumina particles and a thin PTFEcoating.

The surface functionalization of the PNNL sampler has chemicalselectivity for TNT and other nitroaromatics to provide better chemicaluniformity. Selectivity and affinity further improve analyticalperformance. Thermal conductivity can be further enhanced by addingsmall amounts of highly thermal conductive materials, such as Al₂O₃nanoparticles, into the core substrate. It has thermal conductivityaround 30 W/m-K. Performance of rigid samplers for 10 ng TNT (handspike) detection using IMS in negative mode. Data was taken in aBarringer IONSCAN 400A ion mobility spectrometer (Smiths Detection). Theinstrument was operated in negative ion mode at a desorber temperatureof 180° C. and a collection time of 10 s. The drift and inlettemperatures for the IMS were set at 114° C. and 240° C., respectively.The sample gas was set at 239 mL/min and the drift gas at 351 mL/min, asper standard IMS instrument settings.

Example Eleven

The verification of compliance with various nuclear materialrestrictions applicable to certain nation-states and/or monitoring ofnuclear processes for safety or other reasons typically involvedcollection of a substance with a sampler and liquid extraction of thesubstance from the sampler to provide a substance sample in solution.From this solution, the sample may be further prepared and/or submittedfor evaluation by detection instrumentation suitable toidentify/quantify uranium content and/or other nuclear material ofinterest. Such instrumentation includes, but is not limited toInductively Coupled Plasma Mass Spectroscopy (ICP-MS). As reflected inTable VII, this experimental example tests a PTFE-coated/glass coresampler as applied to nuclear material per operation 718 of FIG. 8 andaccompanying text. The relative chemical inertness of PTFE is attractiveas a sampler coating because it generally accommodates a wider selectionof chemicals and procedures for liquid extraction and analysis ofnuclear materials than less chemically inert coatings, and has furtheradvantages as established in Experimental Example Twelve hereafter.

Table VII shows extraction percentage of selected uranium compoundsobtained with a PTFE-coated sampler for each of several differentextraction agents—most of these agents were applied at two or moredifferent molar (M) concentrations of the same active constituent.Namely, three different nitric acid (HNO₃) concentrations were tested(0.0001M, 0.01M, and 6M aqueous solutions), two different sodiumcarbonate (Na₂CO₃) concentrations were tested (0.1M and 1.0M aqueoussolutions), and two different concentrations of an equal molar mixtureof ammonium carbonate and hydrogen peroxide ((NH₄)₂CO₃/H₂O₂) were tested(1.0M/1.0M and 2.0M/2.0M aqueous solutions). For Experimental ExampleEleven, four different chemical forms of uranium were tested to providea more representative scenario of the different types of samplesencountered during field collection. Uranium oxide, U₃O₈ or UO₂ wastested, which are crystalline compounds with relatively low solubilityin water. Uranium Ore Concentrate (UOC) was also tested, which ischaracteristically a uranium mill product containing a highconcentration (at least 90%) of uranium oxide U₃O₈. Also tested wasUranyl fluoride (UO₂F₂), which is a decomposition product that formsfrom the reaction of moisture and uranium hexafluoride (UF₆). The finalcompound tested was uranyl nitrate (UO₂(NO₃)₂), which is sometimesencountered in the reprocessing of spent fuel.

Different uranium compounds each can have a different solubility withrespect to the same solution. A relatively weak acid solution (0.01 MHNO₃) provided suitable extraction and solubility of UO₂F₂ andUO₂(NO₃)₂, while a stronger solution (i.e. (NH₄)₂CO₃/H₂O₂ (2 M)) moresuitably provided for complete extraction of U₃O₈ and UOC. The U₃O₈ formof uranium (including typical yellow cake) exhibited the greatestchemical stability (and associated resistance to extraction) even with a6M nitric acid concentration. Based on these empirical observations, itis fair to surmise that with extended extraction times, a higher acidconcentration, and/or a different agent that 100% extraction ofU₃O₈/yellow cake could be approached, as exemplified by the test resultsfor the U₃O₈/yellow cake extracts provided with the (NH₄)₂CO₃/H₂O₂ (2 M)mixture. Average extraction percentage was calculated from triplicatesamples. The PTFE-coated samplers were in contact with extractionsolutions for approximately 18 hours. Relatively fast kinetics wereobserved for anthropogenic compounds (i.e., UO₂F₂, UO₂(NO₃)₂). In fact,rapid kinetic dissolution rates of uranyl nitrate and uranyl fluoridefrom PTFE-coated glass core removed about 80-100% within 60 minutesunder certain conditions. PTFE-coated sampler testing was performed witha DSA brand, commercially available swipe—the test results were capturedin Table VII as follows:

TABLE VII % Average Extraction Efficiency Extraction Solution U₃O₈ UOCUO₂F₂ UO₂(NO₃)₂ Deionized Water 3 38 24 49 HNO₃ (0.0001M) 3 17 38 44HNO₃ (0.01M) 49 65 97 100 HNO₃ (6.0M) 70 73 100 100 Na₂CO₃ (0.1M) 49 1895 90 Na₂CO₃ (1.0M) 58 79 100 100 (NH₄)₂CO₃/H₂O₂ (1M) 100 72 94 100(NH₄)₂CO₃/H₂O₂ (2M) 98 100 100 96

Example Twelve

Uranium/uranium compound sample preparation traditionally has involvedacquisition with a cotton fabric swipe. Sample extraction from a cottonswipe has proven rather labor-intensive, extending a day or more in somecases. In this experimental example, a range of different uraniumextraction agents were tested comparatively with both a TEXWIPE 304cotton swipe and a PTFE-coated glass core sampler of the type used inExperimental Example Eleven, which demonstrated various differencesleading to the unexpected, surprise discovery of several advantages ofthe PTFE-coated sampler. The TEXWIPE 304 swipe is a double-sidedtwill-pattern cotton wiper purportedly woven in a cross section of118×60 threads per square inch with long staple cotton yarn under cleanroom conditions, and reportedly has cellulose fibers with a relativelylow level of naturally occurring uranium. Extraction and analysis ofdeposited uranium compound particles on PTFE samplers were achieved inhours, or up to a day for hard mineral compounds. In contrast,pre-existing cotton swipe schemes take many more chemical steps and moretime (with corresponding labor cost increases) to analyze uraniumparticles with standard protocols.

Table VIII presents basic extraction efficiency results that showsbetter recovery of analyte from the PTFE-coated sampler than the TEXWIPE304 cotton swipe for most tested conditions. These test resultsconfirmed prior understanding that the TEXWIPE 304 composition has poorefficiency with respect to some of the listed extraction solutions, butthe performance of a PTFE-coated sampler was largely unknown before thisexperimentation. In addition to the four different chemical forms ofuranium submitted to extraction in Experimental Example Eleven,Experimental Example Twelve also tested extraction efficiency for uranylorthophosphate, (UO₂(HPO₄)*4H₂O), which is also known by theabbreviation “HUP.”

Per Table VIII, the applied extraction agents were weak and strongnitric acid (0.01 and 6 M aqueous solutions), sodium carbonate (1 Maqueous solution), and acetone (laboratory grade purity). The highestconcentration of HNO₃ acid used (6.0 M) displayed the greatestextraction percentage; however, the increased performance of 6.0 Mnitric acid relative to 0.01 M HNO₃ for the extraction of differentchemical forms of uranium from the TEXWIPE 304 was generally marginalfor all but U₃O₈. U₃O₈ extraction removal from both swipe materialsexhibited the lowest efficiency, which corresponds to the relativelystrong kinetic and thermodynamic stability and slower dissolutionkinetics of this compound—resulting in a relatively high extractionresistance—even when subjected to 6.0 M nitric acid. Like ExperimentalExample Eleven, it is reasonable to conclude that with extendedextraction times and stronger acid(s), 100% extraction could beobtained. Correspondingly, a PTFE-coated sampler may enable recovery ofuranium analytes of interest (e.g., by acidic leaching) withoutrequiring total digestion of the sampler material under certaincircumstances.

Acetone is a polar high-volatility organic solvent. In part, theselection of acetone as an extraction agent was because of itsrelatively high volatility under standard temperature and pressureconditions, so that it provided concentrated uranium-bearing solidsafter its quick and relatively easy evaporation. The resulting soliduranium extract was a form more suitable for certain subsequentanalytical techniques; however, it should be appreciated dissolution isstill required typically to perform ICP-MS. While the data in Table VIIIindicates that uranium extraction with acetone from the PTFE-coatedsampler is slightly more effective than the cotton TEXWIPE 304 swipe,the extraction efficiency for acetone relative to the other extractionagents was consistently less:

TABLE VIII % Extraction^(c,d) Swipe 0.01M 6.0M 1.0M Material UCompound^(a,e) HNO₃ HNO₃ Na₂CO₃ Acetone TEXWIPE U₃O₈ 47 58 58 44 304 UOC64 70 70 43 UO₂F₂ 86 100 100 50 UO₂(HPO₄)*4H₂O 100 100 100 57 UO₂(NO₃)₂^(b) 84 100 100 37 PTFE- U₃O₈ 49 70 58 43 Coated UOC 65 73 100 48Fiberglass UO₂F₂ 97 100 100 48 UO₂(HPO₄)*4H₂O 100 100 100 63 UO₂(NO₃)₂^(b) 100 100 100 64 ^(a)The uranium was spiked onto the swipe materialsfrom a Dimethyl Sulfoxide (DMSO) suspension and allowed to air dry.^(b)Uranium in 2% HNO₃ instead of DMSO. ^(c)The concentrations andextraction of uranium were determined via ICP-MS detection of ²³⁸U.^(d)The extraction was performed by placing the spiked swipes in 5 mL ofextractant and continually shaken for approximately 18 hours at roomtemperature. ^(e)U₃O₈ is a stable, common form of uranium oxide commonlyfound in nature; UOC is a commercial, uranium mill product high in U₃O₈;UO₂F₂ is a hydrolysis product of UF₆ that is water soluble anddecomposes to U₃O₈ at 300° C.; UO₂(HPO₄)*4H₂O is a naturally occurringuranium complex corresponding to strong uranium immobilizationproperties of different phosphate minerals; and UO₂(NO₃)₂ is preparedfrom uranium salts treated with nitric acid.

The progressive dissolution of UO₂NO₃, UO₂F₂ and U₃O₈ into nitric,sodium carbonate, and ammonium carbonate/peroxide solutions over time isgraphically shown in FIGS. 26-28, respectively. Aliquots were takenperiodically from each sample vial, which contained spiked swatches ofswipe material submerged in extraction solution. Growth functions wereapplied to each data set to generate non-linear curve fits that depictthe trend of uranyl release in each extraction solution. It should beappreciated that uranyl fluoride and uranyl nitrate are rapidly removedfrom PTFE-coated samplers. Between 80 and 100% extraction of uranylfluoride and uranyl nitrate was achievable in less than 10 minutes usingan aqueous solution including a mixture of (NH₄)₂CO₃ and H₂O₂ in equalmolar amounts to provide a rinsing agent. This result correlates to thedata collected for the same dissolution study done with TEXWIPE 304sampling material.

Example Thirteen

A gas-phase chemical reaction synthesized PTFE for submission to uraniumbackground content testing. From such a source, it has been discoveredthat PTFE can have some of the lowest metal (e.g., uranium) backgroundsrelative to commercial sampling materials. Experimentally, backgroundlevels of uranium for different PTFE-coated samplers was found highlydependent on the sampler source. A pretreatment acid wash of thePTFE-sampler materials was found to reduce background levelssubstantially, with some as low as 0.05 nanogram (ng) of uranium persampler. Preparation of PTFE-coated glass fabric samplers for thisexperimentation proceeded under clean laboratory conditions withassiduous contamination control—and included deposition of highly purePTFE nanoparticles from colloidal suspension on the glass fabricfollowed by calcination to form a hydrophobic microcrystalline surfacelayer. These samplers were found to have the lowest uranium backgroundof any PTFE-coated sampler material tested.

Empirical investigation further included rinsing a batch of TEXWIPE 304swipes five (5) successive time with ultrapure nitric acid (6.0 M) toleach uranium therefrom. After each rinse, ICP-MS instrumentationprovided measurements of the remaining background uranium. Thesemeasurements of the TEXWIPE 304 swipe material with each successive acidrinse were: 0.55, 0.036, 0.028, <0.010, <0.010 nanogram per gram (ng/g)of sampler material, respectively. Table IX summarizes these testresults, comparing them to two different PTFE-coated sampling materialsalso submitted to successive rinsing with concentrated nitric acid (6.0M) five (5) times and corresponding background uranium measurement.Background uranium of TEXWIPE 304 swipes was found to be marginal afterjust a few acid treatments, and was found negligible in samples of purePTFE even after just one rinse. By contrast, commercially-sourcedPTFE-coated fiberglass fabric sampler materials displayed much higheruranium background levels, which, at least in part, is theorized toresult from formation by sintering PTFE powder to the fabric. Incontrast, the laboratory preparation of in-house PTFE-coated fiberglassfabric samplers (parenthetically designated by “PNNL” in the Table IXstudy results) included dip-coating lower-mass fiberglass in a colloidalsuspension of PTFE micro/nanoparticles and then thermally curing in afurnace. Per Table IX, contamination-controlled PTFE preparation andhandling conditions achieved a lower uranium background, as follows:

TABLE IX Acid Leached Uranium* (ng/g material) Swipe Materials 1^(st)rinse 5^(th) rinse TEXWIPE 304 0.55 (+/−0.3) <0.010 Pure PTFE <0.010<0.010 PTFE-coated Fiberglass (PNNL)  1.8 (+/−0.2) <0.010 CommercialPTFE-coated 271-405 140-150 Fiberglass *During cleaning process, allmeasurements in triplicateIn a further aspect of the Experimental Example Thirteen investigation,it also was discovered that solutions of ammonium carbonate/hydrogenperoxide, explored for sampler extraction and rinsing, removedimpurities from PTFE-coated sampler material. The combination ofammonium carbonate and a strong oxidizing agent (such as hydrogenperoxide) in solution, removed surface impurities that tend to causesampler discoloration. For instance, commercially-sourced PTFE-coatedfiberglass fabric samplers were submerged in such a solution for abouttwelve (12) hours, turning the surface color from a beige/tan to white.

Any experiment, theory, thesis, hypothesis, mechanism, proof, example,belief, speculation, conjecture, guesswork, or finding stated herein ismeant to further enhance understanding of the present applicationwithout limiting the construction or scope of any claim that follows orinvention otherwise described herein—except to the extent expresslyrecited in such claim or invention. For any particular reference to“embodiment” or the like, any aspect(s) described in connection withsuch reference are included therein, but are not included in norexcluded from any other embodiment absent reasonable description to thecontrary. For multiple references to “embodiment” or the like, some orall of such references refer to the same embodiment or to two or moredifferent embodiments depending on corresponding modifier(s) orqualifier(s), surrounding context, and/or related description of anyaspect(s) thereof—understanding two embodiments differ only if there issome substantive distinction, including but not limited to anysubstantive aspect described for one but not included in the other. Anyuse of the words: important, critical, crucial, significant, essential,salient, specific, specifically, imperative, substantial, extraordinary,especially, favor, favored, favorably, favorable, desire, desired,desirable, desirably, particular, particularly, prefer, preferable,preferably, preference, and preferred indicates that the describedaspects being modified thereby may be desirable (but not necessarily theonly or most desirable), and further may indicate different degrees ofdesirability among different described aspects; however, the claims thatfollow are not intended to require such aspects or different degreesassociated therewith except to the extent expressly recited, but theabsence of such recitation does not imply or suggest that such aspectsare required to be absent from the claim either. For any method orprocess claim that recites multiple acts, conditionals, elements,gerunds, stages, steps, operations, phases, procedures, or other claimedfeatures; no particular order or sequence of performance of suchfeatures is thereby intended unless expressly indicated to the contraryas further explained hereinafter. There is no intention that methodclaim scope (including order/sequence) be qualified, restricted,confined, limited, or otherwise influenced because: (a) themethod/process claim as written merely recites one feature before orafter another; (b) an indefinite article accompanies a method claimfeature when first introduced and a definite article thereafter (orequivalent for method claim gerunds) absent compelling claimconstruction reasons in addition; or (c) the claim includesalphabetical, cardinal number, or roman numeral labeling to improvereadability, organization, or other purposes without any expressindication such labeling intends to impose a particular order. Incontrast, to the extent there is an intention to limit a method/processclaim to a particular order or sequence of performance: (a) ordinalnumbers (1st, 2nd, 3rd, and so on) or corresponding words (first,second, third, and so on) shall be expressly used to specify theintended order/sequence; and/or (b) when an earlier listed feature isreferenced by a later listed feature and a relationship between them isof such a type that imposes a relative order because construingotherwise would be irrational and/or any compelling applicable claimconstruction principle(s) support an order of the earlier feature beforethe later feature. However, to the extent claim construction imposesthat one feature be performed before another, the mere ordering of thosetwo features is not intended to serve as a rationale or otherwise imposean order on any other features listed before, after, or between them.Moreover, no claim is intended to be construed as including a means orstep for performing a specified function unless expressly introduced inthe claim by the language “means for” or “step for,” respectively. Asused herein, “portion” means a part of the whole, broadly including boththe state of being separate from the whole and the state of beingintegrated/integral/contiguous with the whole, unless expressly statedto the contrary. Representative embodiments in the foregoing descriptionand other information in the present application possibly may appearunder one or more different headings/subheadings. Suchheadings/subheadings go to the form of the application only, which whileperhaps aiding the reader, are not intended to limit scope or meaning ofany embodiments, inventions, or description set forth herein, includingany claims that follow. Only representative embodiments have beendescribed, such that: acts, additions, advantages, alterations,apparatus, aspects, benefits, changes, components, compositions,constituents, deletions, devices, embodiments, equivalents, features,forms, implementations, materials, methods, modifications, objects,operations, options, phases, processes, refinements, steps, stages,structures, substitutions, systems, techniques, and variations that comewithin the spirit, scope, and/or meaning of any inventions definedherein, including any of the following claims, are desired to beprotected.

1-21. (canceled) 22: A method of making a sampler, comprising: providinga sampler fiber core comprised of one or more of: glass, metal,metalloid, inorganic oxide, ceramic, and glass-ceramic; applyingnanoparticles of one or more types of inorganic metallic material to thefiber core to at least partially fill the core; after the applying ofthe nanoparticles to the fiber core, preparing the sampler for use withdetection equipment. 23: The method of claim 22, in which the preparingof the sampler includes depositing a polymer on the fiber core and thenanoparticles, the polymer being comprised of one or more of: polymericorganofluorine, polyimide, polyimide, PFSA, PBI, PDMS, and PPPO, and thenanoparticles are comprised of one or more of: metal, metal oxide, andcarbon. 24: The method of claim 23, in which the depositing of thepolymer includes providing a first polymer layer on the core and asecond polymer layer on the first polymer layer, and composition of thefirst polymer layer being different from the second polymer layer. 25:The method of claim 23, in which the depositing of the polymer includesproviding a first polymer layer on the core and a second polymer layeron the first polymer layer, composition of the first polymer layer andthe second polymer layer both include PTFE, and polymer content of thesampler is in the range of about 20% wt through about 40% wt relative toweight of the sampler with the polymer applied thereto. 26: The methodof claim 23, which includes performing a silanization functionalizationof at least a portion of the fiber core and the nanoparticles before thedepositing of the polymer. 27: The method of claim 22, in which thepreparing of the sampler includes: applying a liquid dispersion ofpolymer particles on the core and the nanoparticles to deposit polymerthereon, the polymer being one or more of: perfluorocarbon,perfluoroether, ETFE, ECTFE, THV copolymer, PVdF, FEP, PCTFE, PVF,PTRFE, poly(vinylidenetetrafluoroethylene) copolymer,poly(vinylidene-trifluroethylene) copolymer, PPBI, PDMS, and PPPO;removing at least a portion of the liquid from the polymer after theapplying of the dispersion to the core; and performing a heat treatmentto prepare the polymer after the applying of the dispersion.